Phase behavior at low oil contents in systems containing anionic surfactants

The transition from liquid crystalline to microemulsion phases has been investigated by adding oil to surfactant—alcohol—brine mixtures in two systems containing anionic surfactants. At high salinities where the surfactant is preferentially soluble in oil, addition of oil first causes transition from a lamellar liquid crystal to a water-continuous isotropic phase which exhibits streaming birefringence and probably contains large, anisotropic micelles. This isotropic phase inverts to an oil-continuous microemulsion as oil content further increases. At somewhat lower salinities just below the “optimum” where the surfactant has equal solubilization capacities for oil and brine, the system passes through three three-phase regions as oil is added. In order of increasing oil content, these consist of two microemulsions in equilibrium with a lamellar liquid crystalline phase, the same two microemulsions in equilibrium with excess brine, and a microemulsion in equilibrium with excess oil and excess brine.     

Investigations into the formation and characterization of microemulsions. I. Phase diagrams of the ternary system water—sodium alkyl benzene sulfonate—hexanol and the quaternary system water—xylene—sodium alkyl benzene sulfonate—hexanol

The phase diagrams of the ternary system water—sodium alkylbenzene sulfonate (NaDBS)-hexanol and the quaternary system water—xylene—NADBS—hexanol have been established at three different temperatures, namely 25, 37, and 50°C. The different phases formed have been qualitatively examined using optical (phase contrast and polarizing) microscopy. The textures of the various liquid crystalline phases in the ternary system have been identified, by comparison with previous studies in the literature. Some of the liquid crystalline phases have been quantitatively assessed using low angle X-ray diffraction. The latter measurements were also used to determine the unit cell dimensions in the various phases studied. With the quaternary system, particular attention was paid to the transparent region which consisted of an L₂ (inverse micellar) phase extending into another transparent region which has a blue “tinge” in some cases, namely the microemulsion (M) region. The amount of water solubilized in the L₂ (reverse micelle) or M + L₂ phase was calculated from the phase diagrams. With the ternary system the results showed a maximum in moles of water solubilized per mole total surfactant (NaDBS + hexanol) at a concentration of 0.3 mole surfactant, at an optimum molar ratio of n-hexanol to NaDBS of 4.5:1. This maximum was about twice with the quaternary system, when compared with that of the ternary system, indicating the importance of the role of xylene in solubilization of water by the surfactants. The present investigation has also shown that the extent of the microemulsion region is significantly reduced by increases of temperature when the NaDBS is lower than 15 wt%.     

Remarkable effect of pre‐organization on the self assembly in chiral liquid crystals

In this article, liquid crystal phases possessing a helical molecular assembly, including frustrated three dimensional (3D) structures, are overviewed. Then, the chirality‐originated superstructures in liquid crystals studied by the author are reviewed. The importance of the concept of “pre‐organization” is highlighted, thus, molecular design producing a strong chiral effect has been proposed. Dichiral twin materials have been prepared systematically based on this concept, and correlation between molecular architectures and resulting frustrated liquid crustal phases, such as smectic blue, cubic, tetragonal smectic Q, and sponge phases, has been investigated. An electrically induced anisotropic birefringent structure in the chiral isotropic phase and a photoinduced 3D‐3D phase transition in the smectic Q phase are introduced as possible application on the basis of the frustrated chiral 3D structured liquid crystal phases. A new type of chiral effect inducing the structural anisotropy in the 3D cubic structure of soft material is also described. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 340–355; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900029     

醇对高效氯氟氰菊酯微乳液相图的影响

通过电导率的测定研究了高效氯氟氰菊酯微乳液的结构结构及结构转变。在表面活性剂、高效氯氟氰菊酯环己酮溶液、醇相对含量一定的情况下,当醇为乙醇时,微乳液经历了由W/O到双连续最后到O/W型的变化;当醇为正辛醇时,微乳液经历了由W/O到液晶、双连续最后到O/W型的变化。绘制了不同条件下高效氯氟氰菊酯微乳体系的拟三元相图,讨论了醇种类、醇含量对各类型微乳区形成的影响。结果表明,随着醇碳链的增大,微乳区面积先增大后减小;醇(正辛醇)固定时,随着醇含量增加,微乳区面积先减小后增大。     

Novel phase behaviour in two (smectic/cholesteric) liquid crystal mixtures

The phase behaviours of mixed liquid crystal systems having either Sm/N or Sm/Ch properties have been studied. The (smectic/nematic) binary system formed smectic phases over a wide and much enhanced range of temperature (42 C) and a broad concentration range (0-90 wt %). The ternary smectic/cholesteric system, in appropriate concentration ranges, exhibited the smectic A phase, a TGBA-like twist grain boundary A phase, the cholesteric phase and blue phases. The TGBA-like phase appeared in the cholesteric-smectic phase transition range. Three textures (chiral pitch, fan-shaped and scale-like) for the cholesteric phase of the ternary smectic/cholesteric mixtures were observed in the ranges 0-7, 7-43 and 43 wt % respectively, of cholesteric CB15, in a binary Sm/N mixture.     

十二烷基硫酸钠多相微乳液的研究

十二烷基硫酸钠(SDS)/正丁醇-异丙醇/庚烷/盐水体系可形成多相微乳液,研究了盐浓度、温度对相态的影响,并用小角X衍射、NMR和ESR技术对多相微乳液的结构进行了研究,比较了四相微乳液中两个富表活剂相的区别。结果认为该体系在合适条件下可形成三相及四相微乳液,微乳液中伴随有层状液晶存在。四相微乳液中的两个富表活剂相组成及结构均不同,表现为ESR中TEMPO探针所检测到的微环境不同,以及^2HNMR反映出其组成和H~2O分子所在位置处分子平均有序性也不同。     

Lyotropic liquid crystalline phases in a ternary system of 1-hexadecyl-3-methylimidazolium chloride/1-decanol/water

Lyotropic liquid crystals formed in a ternary system of 1-hexadecyl-3-methylimidazolium chloride ([C16mim]Cl), 1-decanol, and water at 25 degrees C are reported. The hexagonal and lamellar phases were characterized by small angle X-ray scattering and polarizing optical microscopy. In the phase diagram, the system shows two isotropic liquid phases, a hexagonal phase connected to the [C16mim]Cl-water axis, and a lamellar phase in the center. The formation of liquid crystalline phases is believed to arise from a hydrogen-bonded network comprised of an imidazolium ring, anion, 1-decanol, and water. In the liquid crystal, the intercalation of 1-decanol between neighboring [C16mim]Cl molecules favors the appearance of lamellar phases. The phase behavior of the present system is discussed in comparison with a similar ternary system of cetyltrimethylammonium bromide (CTAB).     

Phase behavior of the orange essential oil/sodium bis(2-ethylhexyl)sulfosuccinate/water system

The ternary phase diagram for the orange essential oil (OEO)/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water system was constructed at 25 °C. It indicates a large single phase region, comprising an isotropic water-in-oil (W/O) microemulsion (ME) phase (L₂), a liquid crystal (LC) (lamellar or hexagonal) and a large unstable emulsion phase that separates in two phases of normal and reverse micelles (L₁ and L₂). In this communication the properties of the ME are investigated by viscosity, electric conductivity and small angle X-ray scattering (SAXS) indicating that the isotropic ME phase exhibits different behaviors depending on composition. At low water content low viscous “dry” surfactant structures are formed, whereas at higher water content higher viscous water droplets are formed. The experimental data allow the determination of the transition from “dry” to the water droplet structures within the L₂ phase. SAXS analyses have also been performed for selected LC samples.     

Lyotropic structures in a thermotropic liquid crystal

We have investigated the nature of didodecyldimethylammonium bromide (DDAB)/water aggregates dispersed in 4-n-pentyl-4'-cyanobiphenyl thermotropic liquid crystal (5CB). The structure of this microemulsion has been probed by small-angle neutron and X-ray scattering experiments far above the nematic-to-isotropic phase transition temperature of the solvent. Our data show that the stability of this system is controlled by strong attractive van der Waals interactions between spherical inverted micelles. These interactions also explain why other swollen mesophases in related cosurfactant/DDAB/water/5CB phase diagrams are not observed. When approaching the isotropic-to-nematic phase transition, scattering experiments additionally confirm the predominance of an increasing attractive interaction due to the 5CB paranematic fluctuations.     

The thermally sensitive characteristics of a (smectic LCP/ nematic LC/chiral dopant) ternary composite system

A transition between the transparent smectic A (SmA) phase and the light scattering chiral nematic (N*) phase was realized based on the thermally induced SmA N* phase transition for the homeotropically aligned \[liquid crystalline polymer (LCP)/liquid crystal (LC)/chiral dopant] ternary composite system. The LCP played an important role in increasing the intensity of the light scattering of the heat-induced N* phase. Meanwhile the effects of the composition of the ternary composite system on the thermo-optical characteristics were also investigated.     

Interaction of sodium ions with cationic surfactant interfaces

The thermodynamically stable microemulsion and lamellar phases in the didodecyldimethylammonium bromide/water/n-decane ternary system were explored in the presence of NaBr to gain information on sodium ion-interface interactions. Experimental results, obtained by different NMR techniques, strongly suggest accumulation of sodium ions at the cationic interface. This apparently counterintuitive result is explained by invoking the dispersion potential experienced by the ions near the interface. A mechanism is proposed that can account for the dramatic shrinkage of the microemulsion phase region when an electrolyte is added.     

Synthesis of inorganic gels in a lyotropic liquid crystal medium. I. Synthesis of silica gels in lamellar phases obtained from non-ionic surfactants

Some lamellar phases made with aqueous lyotropic liquid crystals were used as templates for the gelation of a silica inorganic network from tetramethylorthosilicate (TMOS). The aim was to synthesize materials with an anisotropic texture.Lamellar phases were obtained by using non-ionic surfacants. At first, structural, textural and rheological properties of the lamellar phases were studied. Then, the evolution of the system after introduction of the alkoxide, i.e., during the sol-gel transition, was followed by low angle X ray diffraction and rheological measurements. Finally, a textural study of dried gels was carried out.The formation of gels with a lamellar structure was analysed by compressing the total phase diagram (quaternary system) to a ternary system. The hydrolysis and condensation reactions of the TMOS are strongly influenced by the presence of the structured lamellar phase. Gelation seems to happen around the liquid crystal microdomains. A schematic model of gelation is proposed based on experimental observations.     

Nonequilibrium liquid crystalline layered phase stabilized by light

The ability of light to alter/stabilize a particular thermodynamic phase is a power tool to investigate condensed matter from a new dimension. This field of photoinduced phase transitions is currently an important area of research. Being elastically soft and having subtle changes between its many phases a liquid crystal material is an attractive medium to investigate such light-driven phase transitions. The attraction is partly due to the large birefringence changes accompanying these transitions that are useful in developing photonic devices. In all of the cases reported to date, the photoinduced transition always leads to a phase that in any case exists in the thermal cycle. Recently we reported the first exception to such an established phenomenon (Adv. Mater. 2005, 17, 2086). The guest-host ternary mixture consisting of the photoactive azobenzene guest molecules does not exhibit smectic A phase in the absence of UV radiation. However, the smectic A phase is induced and stabilized only in the presence of UV light. In this paper, we map out hitherto unexplored temperature versus UV intensity phase diagrams for various mixtures, which illustrate that light mimics, in a limited sense, the role of a thermodynamic parameter such as, for example, pressure. The threshold UV intensity required to photodrive the appearance of the smectic A phase is seen to have a strong concentration dependence. Our studies also suggest the possibility of observing a double critical point by employing the UV intensity as a fine-tuning parameter.     

Evaporation from an ionic liquid emulsion

The conditions during evaporation in a liquid crystal-in-ionic liquid microemulsion (LC/microEm) were estimated using the phase diagram of the system. The equations for selected tie lines were established and the coordinates calculated for the sites, at which the evaporation lines crossed the tie lines. These values combined with the coordinates for the phases connecting the tie lines were used to calculate the amounts and the composition of the fractions of the two phases present in the emulsion during the evaporation. One of the emulsion phases was a lamellar liquid crystal and high energy emulsification would lead to the liquid crystal being disrupted to form vesicles. Such a system tenders a unique opportunity to study the interaction between vesicles and normal micelles, which gradually change to inverse micelles over bi-continuous structures. The amount of vesicles in the liquid phase versus the fraction liquid crystal was calculated for two extreme cases of vesicle core size and shell thickness. The limit of evaporation while retaining the vesicle structure was calculated for emulsions of different original compositions assuming the minimum continuous liquid phase to be 50% of the emulsion.     

Characterization of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N])∕TX-100∕cyclohexane ternary microemulsion: investigation of photoinduced electron transfer in this RTIL containing microemulsion

In this study we have characterized a ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl- sulfonyl)imide containing ternary nonaqueous microemulsion ([Emim][Tf(2)N]∕∕TX-100∕cyclo- hexane). The phase behavior and dynamic light scattering study show that the [Emim][Tf(2)N]∕TX-100∕cyclohexane three component system can form microemulsion with [Emim][Tf(2)N] as polar core at suitable condition. We have investigated photoinduced electron transfer (PET) using dimethyl aniline as electron donor and several Coumarin dyes as electron acceptor molecules at two different R values (R = [ionic liquid]∕[surfactant]) to observe how the dynamics of the PET rate is affected in this type of confined microenvironment compared to that of the PET dynamics in neat ionic liquid and other pure solvent media. The plot of observed k(q) values with the free energy change (ΔG(0)) for electron transfer reaction shows an apparent inversion in the observed rate as predicted by the Marcus theory.     

Hydrotrope and Hydrotrope-Solubilization Action of Urea in CTAB/n-C5H11OH/H2O System

Urea is found to show the hydrotrope action when the aqueous solubility of surfactant CTAB is enhanced while it will show the hydrotrope-solubilization action when the solubilized amount of n-C₅H₁₁OH in O/W microemulsion and that of water in W/O microemulsion are increased. The mechanism of the hydrotrope-sotubilization action of urea is in fact the increase of the stability of W/O and O/W microemulsion and structural transition from the lamellar liquid crystal phase to the bicontinuous structure.     

Influence of the smectic A-nematic transitional order on the formation of the smectic phases of 4-n-hexyloxybenzylidene-4′-n-butyIaniline and 4-n-butyloxybenzylidene-4′-n-octyIaniline from an electrically deformed nematic phase

Abstract

The crucial role of the smectic A-nematic transitional order for the formation of the smectic A, B and G phases from an electrically deformed nematic phase of the liquid crystal 4-n-hexyloxy-benzylidene-4′-n-butylaniline (6O.4) with a typical smectic A-nematic first order transition and the formation of the smectic A and B phases from an electrically deformed nematic phase of the liquid crystal (4-n-butyloxy-benzylidene-4′-n-octylaniline (40.8) with a smectic A-nematic second order transition has been demonstrated. The nematic phase was deformed by an AC voltage of 2U,_th 5U _th and 10U _th, where U _th is the threshold voltage which causes the appearance of the Fréedericksz transition in the homeotropic nematic layer. The smectic textures have been observed on free cooling of the nematic phase or after the use of an oven. The smectic A phase of the liquid crystal 60.4 was observed with the formation of a clear smectic A-nematic phase boundary while the smectic A phase of the liquid crystal 40.8 has been formed from intermediate pretransitional stripes, observed by Cladis and Torza [1]. The homeotropic anchoring of the direction was crucial for the formation of the smectic phases of the liquid crystal 40.8 but not significant for the liquid crystal 60.4.     

The Hydrotrope Action of Vitamin C

The effects of vitamin C are determined in the oil-in-water(0/ W) and water-in-oil(W/ 0) microemulsion regions of CTAB/ pentanol/ p-xylene/ H20 system. The addition of Vc joins the O/ W and W/ O areas in the phase diagram and expands the bicontinous region by reducing the lamellar liquid crystal one. The results show that the “ coupling action” of Vc is in fact a structural transition from lamellar crystal to isotropic phase with W/ O, O/ W and bicontinous structure.     

Temperature-induced three-phase equilibrium of medium-chain-length poly-3-hydroxyalkanoates-incorporated emulsion system for production of polymeric nanoparticle

The study investigated the effects of temperature on the phase behavior of medium-chain-length poly-3-hydroxyalkanoates (mcl-PHA)-incorporated emulsion system. It is suggested that the three-phase equilibrium consisting of lamellar liquid crystalline (L_a), bi-continuous microemulsion (D), and oil-swollen micelle phases formed in the vicinity of optimal formulation when the combination of phase inversion composition (PIC) and phase inversion temperature (PIT) methods was applied. The interaction effects between two parameters, viz. temperature and mcl-PHA molecular weight, influenced the lamellar/bi-continuous microemulsion formation within the mcl-PHA-incorporated emulsion. It is suggested that the lamellar/bi-continuous microemulsion phase of mcl-PHA-incorporated emulsion can be thermally induced from multiple emulsion system proximately before EIP, and its hypothetical formation mechanism is elucidated in this study.     

Effects of salinity on the viscosity and birefringence of a microemulsion system

Oil/water/surfactant systems form complex equilibrium phases which are sensitive to a number of parameters, including amount and concentration of cosurfactant (often an alcohol), salinity, and temperature. If one of these variables is changed systematically as, for example, the salinity, an interesting transition may be observed in which at low salinities a microemulsion is in equilibrium with an excess oil phase, at moderate salinities a middle phase microemulsion is in equilibrium with both excess oil and excess water phases, and at higher salinities brine is in equilibrium with a microemulsion phase. To help elucidate the structure of the microemulsion, studies of viscoelasticity and streaming birefringence in oscillatory shear flow have been conducted of a middle phase-forming system as a function of salinity. It is found that the viscoelastic properties of the microemulsions are unchanged for shear rates varying from 0.1 to 100 sec⁻¹. Both the birefringence and the viscosity maximize near the salinity marking the transition from lower phase to middle phase microemulsion. Further inflections in these properties occur at a salinity marking the midrange of the middle phase microemulsion. For all cases the dominent relaxation time is near 3 to 5 msec while the birefringence changes by two orders of magnitude. The birefringence is a sensitive indicator of the elastic structure of the microemulsion.