Formation of intermediate micellar phase between hexagonal and discontinuous cubic liquid crystals in brine/N-acylamino acid surfactant/N-acylamino acid oil system.

The phase behavior in the brine/sodium N-dodecanoyl sarcosinate (Sar)/isopropyl N-dodecanoyl sarcosinate (SLIP) system has been investigated by means of phase study, static light scattering, and small-angle X-ray scattering. The liquid crystal phases, hexagonal (H(1)) and discontinuous cubic (I(1)), melt upon the addition of NaCl, which shows the similar effect to the increasing of temperature. The addition of SLIP to the brine/Sar solution at high Sar concentration induces the phase transition from H(1) to I(1) via the isotropic micellar solution (W(m2)). The micellar structure in the W(m2) phase also changes from the wormlike to the globular micelle with SLIP concentration. Adding NaCl reduces the repulsive force between the Sar head groups and simultaneously the space of the solubilized SLIP in the palisade layer, leading SLIP to shift their location further into the micelle core. As a consequence, the hexagonal symmetry breaks into the micelle solution and the liquid crystal order is destabilized entropically.

Foaming properties of monoglycerol fatty acid esters in nonpolar oil systems.

Foaming properties of monoglycerol fatty acid esters that have different alkyl chain lengths were studied in different nonpolar oils, namely liquid paraffin (LP 70), squalane, and squalene. The effect of the hydrocarbon chain length of the surfactant, the concentration, the nature of the oil, and the temperature on the nonaqueous foam stability was mainly studied. Five weight percent of glycerol alpha-monododecanoate (monolaurin) formed highly stable foams in squalane at 25 degrees C, and the foams were stable for more than 14 h. Foam stability of the monolaurin/LP 70 and the monolaurin/squalene systems are almost similar, and the foams were stable for more than 12 h. Foam stability was decreased as the hydrocarbon chain length of the monoglyceride decreased. In the glycerol alpha-monodecanoate (monocaprin)-oil systems, the foams were stable only for 3-4 h, depending on the nature of the oil. However, the foams formed in the glycerol alpha-monooctanoate (monocaprylin)-oil systems coarsened very quickly, leading to the progressive destruction of foam films, and all of the foams collapsed within a few minutes. Foam stability decreased when the oil was changed from squalane to squalene, in both monocaprin and monolaurin systems. It was observed that, in the dilute regions, these monoglycerides form fine solid dispersions in the aforementioned oils at 25 degrees C. At higher temperatures, the solid melts to isotropic single-liquid or two-liquid phases and the foams formed collapsed within 5 min. Judging from the wide-angle X-ray scattering (WAXS) and the foaming test, it is concluded that the stable foams are mainly caused by the dispersion of the surfactant solids (beta-crystal) and foam stability is largely influenced by the shape and size of the dispersed solid particles.

Wormlike micelles in mixed surfactant solutions.

Small micellar aggregates of some surfactants exhibit enormous growth in one dimension and form very long and flexible wormlike micelles. Depending on the nature of the surfactant, such micellar growth can be induced in different ways, for example by adding cosurfactants or salts. Above a system-dependent concentration of surfactant, these giant micelles are entangled to form a transient network, and exhibit viscoelastic behavior analogous to a flexible polymer solution. However, unlike polymers in solutions, wormlike micelles undergo breaking and recombination, and, therefore, exhibit complex rheological behavior. Information on the evolution of aggregate morphology can be obtained from rheological study. In this article formation of wormlike micelles and the evolution of rheological properties in different mixed surfactant systems is discussed. Besides, a brief overview on the salt-induced micellar growth in ionic surfactant systems and reverse micellar systems induced by adding certain polar additives has also been presented.

Phase behavior of monoglycerol fatty acid esters in nonpolar oils: reverse rodlike micelles at elevated temperatures.

We have studied nonaqueous phase behavior and self-assemblies of monoglycerol fatty acid esters having different alkyl chain lengths in different nonpolar oils, namely, liquid paraffin (LP 70), squalane, and squalene. At lower temperatures, oil and solid surfactants do not mix at all compositions of mixing. Upon an increase in the temperature of the surfactant system, the solid melts to give isotropic single or two-liquid phases, depending on the nature of the oil and the surfactant. All monolaurin/oil systems form an isotropic single-phase liquid, but with a decreasing alkyl chain length of surfactant, they become less lipophilic and immiscible in oils. As a result, a two-phase domain is observed in the oil rich region of all monocaprylin/oil systems over a wide range of concentrations. Judging from the phase diagrams, the surfactants are the least miscible with squalane, and the order of miscibility tendency is squalene > LP 70 > squalane. With a further increase of temperature, the solubility of the surfactant in the oil increases, and the two-liquid phase transforms to an isotropic single phase. This phase transformation corresponds to the reverse of the cloud-point phenomenon observed in aqueous nonionic surfactant systems. Small-angle X-ray scattering (SAXS) measurements show the presence of reversed rodlike micelles in the isotropic single phase, and the length of the aggregates decreases with increasing temperature and increasing alkyl chain length of the surfactant. These results indicate a rod-sphere transformation with increasing lipophilicity of the surfactant and confirms the validity of Ninham's penetration model in the reversed system. An addition of a small amount of water dramatically enhances the elongation of the reverse micelles. Increasing the surfactant concentration or changing the oil from squalene to LP 70 also increases the length of the rodlike aggregates.

Disconnected lamellar phases (Lalpha) in pseudobinary water-non-ionic surfactant systems: a general phenomenon.

This study provides new experimental evidence for the disconnection of the lamellar phase (L(alpha)) in pseudobinary water-non-ionic surfactant systems. To prove that the disconnection is indeed a general phenomenon the phase behavior of the pseudobinary system water-pentaethylene glycol dodecyl ether/hexaethylene glycol dodecyl ether (H(2)O-C(12)E(5)/C(12)E(6)) was investigated as a function of the surfactant composition delta and the total surfactant concentration gamma. At a fixed gamma of 0.10 the extension of the highly diluted L(alpha) phase shrank continuously with increasing amount of C(12)E(6), i.e., increasing delta, until it disappeared at delta=0.60. The gamma-T phase diagram of this particular surfactant mixture was found to have a disconnected L(alpha) phase. For the first time, SAXS measurements were carried out to monitor structural changes related to the disconnection. For this purpose the interlayer spacing d and the effective cross-sectional area a(s) were determined from the SAXS data along characteristic paths through the L(alpha) phase.

Aqueous foam stabilized by dispersed surfactant solid and lamellar liquid crystalline phase.

Foaming properties of dilute aqueous solutions of pentaglycerol monostearate (C(18)G(5)) and pentaglycerol monooleate (C(18:1)G(5)) have been studied at 25 degrees C. The aqueous C(18)G(5) system formed highly persistent foams, which did not rupture for several days. Foamability and foam stability were increased on increasing the surfactant concentration in both C(18)G(5) and C(18:1)G(5) systems. The C(18:1)G(5)/water system showed lower foam stability compared to the C(18)G(5)/water system. Aqueous phase behavior of the C(18)G(5) and C(18:1)G(5) systems showed the dispersion of alpha-solid and L(alpha) phase respectively in water rich region at 25 degrees C. Stable foam in the C(18)G(5)/water system was mainly due to the finely dispersed small surfactant solid particles. The average particles diameter of alpha-solid and L(alpha) dispersion is found less than 1 mum and it decreases with increasing surfactant concentration. There is no appreciable difference in the particle size of the alpha-solid and L(alpha) dispersion; however, the foam stability differs largely. Foam stabilized by lamellar liquid crystal dispersion in C(18:1)G(5)/water system, is less stable compared to the foam stabilized by the surfactant solid dispersion in C(18)G(5)/water system. The foamability and foam stability of the surfactant systems show poor correlation with the dynamic surface tension properties.

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.

Phase behavior of diglycerol fatty acid esters-nonpolar oil systems.

Phase behavior of diglycerol fatty acid esters (Qn-D, where n represents the carbon number in the alkyl chain length of amphiphile, n = 10-16) were investigated in different nonpolar oils, liquid paraffin (LP70), squalane, and squalene. There is surfactant solid at lower temperature, and the surfactant solid does not swell in oil, and the melting temperature is almost constant in a wide range of compositions. In all of the systems, a lamellar liquid crystal (L(alpha)) is formed in a concentrated region at a temperature between the solid melting temperature and the isotropic two- or single-phase regions. In the dilute regions, reverse vesicles are formed in L(alpha) + O regions. There are two liquid-phase regions above the L(alpha) present region. This two-phase boundary corresponds to the cloud-point curve of nonionic surfactant aqueous solutions. However, instead of being less soluble in water at high temperature for the cloud point, the surfactant becomes more soluble in the organic solvents at high temperature. Namely, the effect of temperature on the solubility is opposite to the clouding phenomenon. When the hydrocarbon chain of the diglycerol surfactant decreases, the two-phase region becomes wider. In the case of a fixed surfactant, the surfactant is most miscible with squalene (narrowest two-phase regions) and the order of dissolutions tendency is squalene > LP70 > squalane. These results show that the hydrophilic moiety (diglycerol group) is more insoluble in oil compared with that of a conventional poly(oxyethylene)-type nonionic surfactant. Formation of reversed rodlike micelles was confirmed by SAXS scattering curve. When the hydrocarbon chain of surfactant is short, the micellar size becomes larger. In a fixed surfactant system, the reverse micellar size increases by changing oil from squalene to LP70. A small amount of water induces a dramatic elongation of reverse micelles.

Effect of added poly(oxyethylene)dodecyl ether on the phase and rheological behavior of wormlike micelles in aqueous SDS solutions.

Upon the addition of a short EO chain nonionic surfactant, poly(oxyethylene) dodecyl ether (C12EOn), to dilute micellar solution of sodium dodecyl sulfate (SDS) above a particular concentration, a sharp increase in viscosity occurs and a highly viscoelastic micellar solution is formed. The oscillatory-shear rheological behavior of the viscoselastic solutions can be described by the Maxwell model at low shear frequency and combined Maxwell-Rouse model at high shear frequency. This property is typical of wormlike micelles entangled to form a transient network. It is found that when C12EO4 in the mixed system is replaced by C12EO3 the micellar growth occurs more effectively. However, with the further decrease in EO chain length, phase separation occurs before a viscoelastic solution is formed. As a result, the maximum zero-shear viscosity is observed at an appropriate mixing fraction of surfactant in the SDS-C12EO3 system. We also investigated the micellar growth in the mixed surfactant systems by means of small-angle X-ray scattering (SAXS). It was found from the SAXS data that the one-dimensional growth of micelles was obtained in all the SDS-C12EOn (n=0-4) aqueous solutions. In a short EO chain C12EOn system, the micelles grow faster at a low mixing fraction of nonionic surfactant.

Interfacial properties and foam stability effect of novel gemini-type surfactants in aqueous solutions.

Static and dynamic surface tension and interfacial rheological behavior of a novel anionic gemini-type surfactant without a spacer group, sodium 2,3-didodecyl-1,2,3,4-butane tetracarboxylate (GS), were investigated. Very low values for critical micelle concentration (8.9x10(-5) M) as well as equilibrium surface tension (22.7 mN m(-1)) were observed for the aqueous solutions. Dynamic surface tension (DST) is very slow and less sensitive to the surfactant concentration than the conventional monomeric surfactant, suggesting the presence of a significant adsorption barrier for GS owing to a complicated molecular structure. Presence of a small concentration of GS in sodium dodecyl sulfate (SDS) solution shows a synergistic effect to form mixed micelles and lowers the cmc considerably. This synergism between GS and SDS and slow exchange of GS between bulk and interface create a rigid air-liquid interface of the SDS-GS solution, which is reflected in a higher elasticity value for the interface of the SDS-GS solution than for the SDS solution. It has been found that the presence of a small concentration of GS in SDS solution increases the foam stability noticeably. Although the stability of the wet foam is correlated with the film elasticity, the stability of dry foam cannot be explained in terms of film elasticity alone.

Wormlike micelles and microemulsions in aqueous mixtures of sucrose esters and nonionic cosurfactants.

A study of the phase and rheological behavior of sucrose hexadecanoate (C16SE)/cosurfactant/water systems in the presence of solubilized oil, using complementary techniques such as dynamic light scattering and small angle X-ray scattering, is presented. Viscoelastic wormlike micellar solutions are found when a nonionic lipophilic cosurfactant is added to C16SE aqueous systems. Contrary to previous reports, the effect of oil solubilization on these wormlike micelles is not unique and depends on several factors. Linear alkyl chain oils that tend to solubilize in the micellar core have a disrupting effect, decreasing the relaxation time and the viscosity of the systems. This effect is larger as the molecular volume of oil increases and as the solubility of the cosurfactant in oil increases. On the other hand, oils that penetrate in the palisade layer, such as p-xylene, induce micellar growth and have a thickening effect at a given micellar composition. Thermodynamic considerations are used to explain the experimental results.

Phase polymorphism by mixing of poly(oxyethylene)-poly(dimethylsiloxane) copolymer and nonionic surfactant in water.

The phase behavior of the water/poly(oxyethylene)-poly(dimethylsiloxane) copolymer (Si25C3EO51.6)/pentaoxyethylene dodecyl ether (C12EO5) ternary system has been studied. Both the silicone copolymer and the surfactant have equal volumes of hydrophilic and lipophilic parts; i.e., these are balanced amphiphiles. Although only a lamellar phase is observed in water-Si25C3EO51.6 and water-C12EO5 binary systems, a variety of liquid crystalline phases, including normal micellar cubic (I1), hexagonal (H1), bicontinuous cubic (V1), lamellar (L(alpha)), reverse bicontinuous cubic (V2), and reverse hexagonal (H2), are observed in the copolymer-rich region of the ternary phase diagram. The small C12EO5 molecules dissolve at the hydrophobic interface in the thick bilayer of the Si25C3EO51.6 L(alpha) phase occupying a large area of the total interface of the aggregates and modulate the curvature of the aggregates. Hence a variety of self-assembled structures are observed. In contrast, Si25C3EO51.6 is not dissolved in the thin bilayer of the C12EO5 lamellar phase (L'(alpha)). Hence, the C12EO5 L'(alpha) phase coexists with copolymer-rich L(alpha) and H2 phases. Consequently, small surfactant molecules are dissolved in a large silicone copolymer aggregate to induce a change in layer curvature, but a large copolymer molecule is hard to incorporate with surfactant aggregates.

Effects of added nonionic surfactant and inorganic salt on the rheology of sugar surfactant and CTAB aqueous solutions.

The effect of adding tri(oxyethylene) dodecyl ether (C12EO3) on the phase and rheological behavior of sucrose hexadecanoate and CTAB aqueous solutions in the presence of added salt (NaBr) was investigated. Viscoelastic solutions are formed in CTAB and C16SE systems upon addition of lipophilic nonionic surfactant C12EO3. The zero-shear viscosity shows a maximum at a certain mixing fraction of C12EO3, except in the case of the aqueous CTAB/C12EO3 system in the absence of salt. The rheological properties are strongly affected by the addition of salt to the CTAB systems but they remain unaltered in the case of C16SE systems. In ionic systems, the mixing fraction of C12EO3 for the maximum viscosity depends on salt concentration.

Phase behavior of poly(oxyethylene) cholesteryl ether/novel alkanolamide/water systems.

The phase behavior and microstructure of mixed nonionic surfactant systems containing poly(oxyethylene) cholesteryl ether (ChEOn, n=15 and 10), a new alkanolamide-type foam booster, dodecanoyl N -methylethanolamide (NMEA-12), and water, were investigated at 25 degrees C by means of visual observation and small-angle X-ray scattering. In the ChEO(15)/water binary system, aqueous micellar (W(m)), discontinuous cubic liquid crystal (I(1)), hexagonal (H(1)), rectangular ribbon (R(1)), lamellar (L(alpha)), and solid (S) phases are successively formed with increasing surfactant concentration. Although the R(1) phase is an intermediate phase formed in a very narrow composition range in conventional surfactant systems, its domain is unusually wider than that of H(1), which may be attributed to the packing constraint caused by the bulky cholesteric group in the lipophilic core of the aggregate. Upon addition of lipophilic NMEA-12 to the ChEO(15)/water binary system, the interfacial curvature of the aggregates decreases, and the micellar or liquid crystal phases formed in the binary system transform to the reverse micellar (O(m)) phase via the L(alpha) phase existing over a wide concentration range. The SAXS results establish an epitaxial relationship between the (11) plane of the R(1) phase and the (10) plane of the L(alpha) phase. The ChEO(10)/NMEA-12/water system shows a phase diagram of similar general appearance, except that the W(m) to R(1) phase transformation occurs via an optically anisotropic liquid crystal phase of unknown structure and the R(1) to L(alpha) phase transition occurs through a narrow intermediate defected lamellar (L(alpha)(H)) phase. The variation in the aggregate size and shape and the unit cell of the R(1) phase formed in ChEOn/NMEA-12/water systems is also discussed.

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.

Rheology and dynamics of micellar cubic phases and related emulsions.

The rheological behavior of micellar cubic phases in C12EO25 systems and related emulsions has been investigated. In the aqueous C12EO25 binary system, the transition from the cubic phase to the micellar solution is associated with a sudden drop in viscosity and with a small enthalpy of transition. The elastic modulus and viscosity of the cubic phases show a maximum with concentration but remain very high within the range of existence of the cubic phase. Several relaxation processes seem to be present in binary cubic phases, and some of them occur in a time scale that can be followed by both rheology and dynamic light scattering measurements. Upon addition of a small amount of oil (decane), the rheological behavior changes remarkably. As the oil fraction increases, the relaxation times also increase and, finally, highly concentrated, gel-like emulsions are obtained. Contrary to conventional concentrated emulsions, the viscosity of cubic-phase-based emulsions is decreased by increasing the fraction of the dispersed phase. The non-Maxwellian rheological behavior at low oil fractions is described according to the model of slipping crystalline planes, modified by using a distribution of bulk relaxation times, and good fitting to the experimental data is obtained.

Phase behavior of a mixture of poly(isoprene)-poly(oxyethylene) diblock copolymer and poly(oxyethylene) surfactant in water.

The phase behavior of a mixture of poly(isoprene)-poly(oxyethylene) diblock copolymer (PI-PEO or C250EO70) and poly(oxyethylene) surfactant (C12EO3, C12EO5, C12EO6, C12EO7, and C12EO9) in water was investigated by phase study, small-angle X-ray scattering, and dynamic light scattering (DLS). The copolymer is not soluble in surfactant micellar cubic (I1), hexagonal (H1), and lamellar (Lalpha) liquid crystals, whereas an isotropic copolymer fluid phase coexists with these liquid crystals. Although the PI-PEO is relatively lipophilic, it increases the cloud temperatures of C12EO3-9 aqueous solutions at a relatively high PI-PEO content in the mixture. Most probably, in the copolymer-rich region, PI-PEO and C12EOn form a spherical composite micelle in which surfactant molecules are located at the interface and the PI chains form an oil pool inside. In the C12EO5/ and C12EO6/PI-PEO systems, one kind of micelles is produced in the wide range of mixing fraction, although macroscopic phase separation was observed within a few days after the sample preparation. On the other hand, small surfactant micelles coexist with copolymer giant micelles in C12EO7/ and C12EO9/PI-PEO aqueous solutions in the surfactant-rich region. The micellar shape and size are calculated using simple geometrical relations and compared with DLS data. Consequently, a large PI-PEO molecule is not soluble in surfactant bilayers (Lalpha phase), infinitely long rod micelles (H1 phase), and spherical micelles (I1 phase or hydrophilic spherical micelles) as a result of the packing constraint of the large PI chain. However, the copolymer is soluble in surfactant rod micelles (C12EO5 and C12EO6) because a rod-sphere transition of the surfactant micelles takes place and the long PI chains are incorporated inside the large spherical micelles.

A novel anionic surfactant templating route for synthesizing mesoporous silica with unique structure.

Anionic surfactants are used in greater volume than any other surfactants because of their highly potent detergency and low cost of manufacture. However, they have not been used as templates for synthesizing mesoporous silica. Here we show a templating route for preparing mesoporous silicas based on self-assembly of anionic surfactants and inorganic precursors. We use aminosilane or quaternized aminosilane as co-structure-directing agent (CSDA), which is different from previous pathways. The alkoxysilane site of CSDA is co-condensed with inorganic precursors; the ammonium site of CSDA, attached to silicon atoms incorporated into the wall, electrostatically interacts with the anionic surfactants to produce well-ordered anionic-surfactant-templated mesoporous silicas (AMS). These have new structures with periodic modulations as well as two-dimensional hexagonal and lamellar phases. The periodic modulations may be caused by the coexistence of micelles that differ in size or curvature, possibly owing to local chirality. These mesoporous silicas provide a new family of mesoporous materials as well as shedding light on the structural behaviour of anionic surfactants.

Effect of ionic surfactants on the phase behavior and structure of sucrose ester/water/oil systems.

The phase behavior and structure of sucrose ester/water/oil systems in the presence of long-chain cosurfactant (monolaurin) and small amounts of ionic surfactants was investigated by phase study and small angle X-ray scattering. In a water/sucrose ester/monolaurin/decane system at 27 degrees C, instead of a three-phase microemulsion, lamellar liquid crystals are formed in the dilute region. Unlike other systems in the presence of alcohol as cosurfactant, the HLB composition does not change with dilution, since monolaurin adsorbs almost completely in the interface. The addition of small amounts of ionic surfactant, regardless of the counterion, increases the solubilization of water in W/O microemulsions. The solubilization on oil in O/W microemulsions is not much affected, but structuring is induced and a viscous isotropic phase is formed. At high ionic surfactant concentrations, the single-phase microemulsion disappears and liquid crystals are favored.

Phase behavior of polyglycerol didodecanoates in water.

A phase diagram of a water-polyglyceryl didodecanoate ((C11)2Gn) system was constructed as a function of polyglycerol chain length (n) at 25 degrees C. The average number of dodecanoic acid residues attached to polyglycerol is in the range of 1.6-2.3, and unlike commercial long-chain polyglycerol surfactants, unreacted polyglycerols were removed in the surfactants used. With an increase in the polyglycerol chain, the surfactant changes from lipophilic to hydrophilic, and the type of self-organized structure also changes from lamellar liquid crystals to the aqueous micellar solution phase via hexagonal liquid crystals. However, a discontinuous micellar cubic phase does not appear in the phase diagram, while it is formed in a long poly(oxyethylene)-chain nonionic surfactant system. In a dilute region, a cloud point is observed at a moderate polyglycerol chain length, n approximate to 7. The cloud temperature is dramatically increased with a slight increase in hydrophilic chain because the dehydration of the hydrophilic chain length at high temperature is low compared with that of the poly(oxyethylene) chain. In other words, the phase behavior of (C11)2Gn is not very temperature sensitive. Three-phase microemulsion is formed in a water/(C11)2.3G7.3/m-xylene system. The three-phase temperature or HLB temperature is highly dependent on the polyglycerol chain length.