Molecular orientation of lyotropic nematic phase in a mixture of two non-mesogenic compounds

We report the results of our studies on the optical and thermal properties of the mixture of two non-mesogenic compounds, namely, sodium dodecyl sulfate (SDS) and glacial acetic acid (GAA). The mixture exhibits very interesting schlieren texture of lyotropic micellar nematic (N_D) phase, SmA and SmB phases, respectively, at different concentrations of SDS in GAA sequentially when the specimen is cooled from its isotropic phase. The order parameter (S) of the lyotropic micellar nematic (N_D) phase is estimated with the help of temperature dependence of optical anisotropy from the measured values of refractive index and density data. The experimental curve showing the temperature variation of order parameter is very well fitted with the Mayer–Saupe theoretical curve. X-ray studies have also been discussed. The formation of the above phases has been confirmed by optical and differential scanning calorimetry studies.     

Micellar shape anisotropy on lyotropic nematic phases

In this work we show, that with the introduction of the micellar shape anisotropy in the order parameter of a lyotropic liquid crystal, it is possible to understand, in a unified way, the features observed in the phase diagram of these materials. Using the de Gennes connection between microscopic and macroscopic order parameters, such an extended order parameter is constructed from a geometrical conception of the micelles. Our theoretical results will be correlated with refractive index experimental data near the uniaxial-biaxial nematic phase transitions of a lyotropic mixture of potassium laurate, decanol and deuterium oxide.     

Lyotropic mixture made of potassium laurate/1-undecanol/K2SO4/water presenting high birefringences and large biaxial nematic phase domain: a laser conoscopy study

The lyotropic liquid crystalline quaternary mixture made of potassium laurate (KL), potassium sulphate, 1-undecanol and water was investigated by experimental optical methods (optical microscopy and laser conoscopy). In a particular temperature and relative concentrations range, the three nematic phases (two uniaxial and one biaxial) were identified. The biaxial domain in the temperature/KL concentration surface is larger when compared to other lyotropic mixtures. Moreover, this new mixture gives nematic phases with higher birefringence than similar systems. The behavior of the symmetric tensor order parameter invariants σ (3) and σ (2) calculated from the measured optical birefringences supports that the uniaxial-to-biaxial transitions are of second order, described by a mean-field theory.     

The elusive thermotropic biaxial nematic phase in rigid bent-core molecules

The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(p-hydroxyphenyl)-l,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D_2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.     

Chromonic liquid crystalline phase transition involving a biphasic region of nematic and hexagonal phases

We report the results of our studies on the optical and thermal properties of binary mixture of two compounds viz. abietic acid and poly ethylene glycol (PEG). The mixture shows a very interesting co-existent biphasic region of lyotropic nematic (N + I) and intermediate hexagonal (M + I) phases, sequentially when the specimen is cooled from its isotropic phase at different concentrations of abietic acid in PEG. The aggregated molecular size has been confirmed by X-ray studies. The temperature variation of optical anisotropy, electrical conductivity, ultrasonic velocity, and molar and adiabatic compressibility has also been discussed.     

Orientational diffusivities measured by Rayleigh scattering in a lyotropic calamitic nematic () liquid crystal phase: the backflow problem revisited

Using a light-beating technique we have measured the damping time of thermal fluctuations of the nematic director for the so called cylindrical or calamitic nematic (N_C) phase of the lyotropic system K-laurate/decanol/. By varying the scattering angle in suitable geometries, we have been able to estimate the orientational diffusivities associated to the three pure deformations of splay, twist and bend. A former measurement made in the disk-like N_D phase of the same system yielded a large deviation between the splay and twist diffusivities. The effect was then attributed to induced flows, or backflow, which could be responsible for the reduction of the splay viscosity. In fact, this is the analogous effect, for disks, to the one recognized since long time ago arriving for rod-like molecules in a classical nematic, though in this case it is associated with bend deformations. The analogy comes about thanks to the interchange of the role played by disks and cylinders for, respectively, splay and bend fluctuations.The measurements reported here provide a new test on the applicability of the backflow model to a nematic system composed of micelles, that is, aggregates made of amphiphilic (surfactant) molecules, in its cylindrical-like variant, i.e. the N_C phase. In addition, the comparative study made here with the previous results existing in the literature for the N_D phase, allows us to conjecture on structural issues concerning lyotropic nematics. Received: 29 April 1998 / Revised: 19 August 1998 / Accepted: 31 August 1998     

Polarizing Microscopic and 31P NMR Studies of Decylammonium Chloride/Potassium Chloride/Water System. Containing Phosphoric Acid Monodecyl Ester and H3PO4

The decylammonium chloride (DACl), KCl and D₂O system forms two phases(N_c+N_d) in the nematic range. The N_d phase was ca. 15% by volume and exhibited extinct appearance. From conoscopic measurements it was inferred that the optical axis of the N_d phase was tilted. The lamellar phase of the DACl-KCl-D₂O system as well as the lamellar phase obtained by adding phosphoric acid decylester/phosphoric acid (PDE/H₃PO₄) showed the following phase sequence: L_α + N_d 35°C H_α + N_d 40°C N_c + N_d 45°C N_c 50°C isotropic The line shapes of ³¹P NMR of PDE/H₃PO₄ were found to be sensitive to micelle size and dynamics occuring in the lyotropic system, but they do not differentiate between different micelle shapes.     

Correlation of the molecular structure of discotic nematic liquid crystals with their orientational order and specific features of the nematic-isotropic phase transition

The orientational order parameter S of molecules in high-temperature discotic nematic liquid-crystal phases of triphenylene derivatives is investigated as a function of the length of side flexible molecular chains at different temperatures. It is established that the orientational order parameters S in the range of the transition from the nematic phase to the isotropic liquid phase (the N _D -I transition) are smaller than those predicted from the molecular-statistical theory and computer simulation. It is shown that the N _D -I transition is close to both the isolated Landau point and the tricritical point (regardless of the chemical structure of the molecules and the anisotropy of dispersion intermolecular interactions). Consistent explanations are offered for a number of experimental findings, such as the anomalously small changes in the enthalpy and entropy upon the N _D -I transition (as compared to those revealed upon the N-I transition in calamitic nematic liquid crystals), the anomalously strong response of the isotropic phase of discotic nematic liquid crystals to external fields (thermodynamically conjugate to the order parameter S) and the long relaxation times of this response, and the formation of cybotactic discotic molecular clusters in the isotropic phase in the vicinity of the N _D -I transition.     

Orientational order parameter studies in two symmetric dimeric liquid crystals – an optical study

The optical technique developed by [W. Kuczynski, B. Zywucki, and J. Malecki, Determination of orientational order parameter in various liquid-crystalline phases, Mol. Cryst. Liq. Cryst. 381 (2002), pp. 1–19; B.J. Zywucki and W. Kuczynski, IEEE transactions on optical phenomena – The orientational order in nematic liquid crystals from birefringence measurements, Dielectr. Electr. Insul. 8 (2001), pp. 512–515] is fabricated and used to determine the orientational order parameter in two dimeric liquid crystalline compounds nematic and SmA phases of α,ω-bis(4-alkylanilinebenzylidene-4′-oxy)alkane (m.OnO.m) homologous series. The compounds studied are 5.O8O.5 and 5.O10O.5 which exhibit nematic and SmA, and nematic phases, respectively. The orientational order parameter in both the phases of nematic and SmA phases of the compound one and the nematic phase of the compound two are obtained using the principle of Newton's rings which gives directly the birefringence, δn of the liquid crystal dimer. The merits of the technique used are presented over the conventional techniques for the determination of orientational order parameter. The results for the two compounds are compared with those values estimated from n _e, n _o and density using the two internal field models due to Vuks and Neugebauer applicable to nematic phase.     

Effect of the inorganic salt on the electrical conductivity characteristics of lyotropic nematics

The effect of inorganic salt on temperature dependent changes of the electrical conductivity of N_d and N_c lyotropic nematic mesophases consisting of disc like and rod like micelles has been investigated. It has been found from the temperature dependence of the electrical conductivity that the lyotropic and thermotropic phase transitions shifted to lower temperatures by addition of NH₄Br. Addition of the salt stimulates the formation of oriented textures of N_d and N_c mesophases. This work has been supported by EGE-AFP:97 Fen 010 prj.     

Reentrant isotropic-calamitic nematic phase transition in potassium laurate-decanol- D<Subscript>2</Subscript>O mixtures

The phase diagram is an interesting field of research, particularly in lyotropic liquid crystals (LLC). In this way, one of the most important phase diagrams of this LLC system was reported by Yu and Saupe. Two uniaxial (calamitic--N(C) and discotic--N(D)) and one biaxial nematic (N(B)) phases were determined by these authors. Furthermore, in this phase diagram the classical isotropic phase (I was observed at high temperature as well as a reentrant isotropic phase (I(RE)) which takes place at lower temperature. Later, this phase diagram was also studied by several authors and in all cases the I(RE)-N(C)-I phase transitions were not observed. In this work, we present a study of this phase diagram through digital image processing and refractometry optical techniques. The occurrence of these phase transitions is investigated and characterized. In addition, the order parameter is obtained based on the Vuks hypothesis from a particular point, in the range of the N(C) phase, where the absolute value of the optical birefringence (Deltan is maximum.     

Transitions in lyotropic liquid crystals caused by concentration change and γ-radiation

A molecular-statistical theory of phase transitions in lyotropic liquid crystals, which describes the phase transitions between the isotropic (micellar), nematic and lamellar phases was developed. The equations describing the dependence of parameters of orientation and translational long-range order on the concentration were obtained. It was shown that depending on the values of the model microscopic constants, the nematic phase–lamellar phase transition can be both of the first and the second order. The influence of intensive and low intense γ-radiation on the phase transitions mentioned herein was considered. It was shown that the irradiation changes the model constants responsible for the phase transitions. On this basis, it can be assumed that the γ-radiation influences the course of the dependence of the long-range order parameters on concentration as well as it changes the values of the critical concentrations of the phase transitions and even the phase transition order.     

Molecularengineering of discotic nematic liquid crystals

Connecting two columnar phase forming discotic mesogens via a short rigid spacer leads to the formation of a π-conjugated discotic dimer snowing discotic nematic (N _D) phase. Attaching branched-alkyl chains directly to the core in hexaalkynylbenzene resulted in the stabilisation of N_D phase at ambient temperature. Pentalkynylbenzene derivatives possessing a combination of normal- and branched-alkoxy chains display a very broad N_D, phase which is stable well below and above the room temperature.     

Lamellar-to-nematic phase transition in a lipid-surfactant mixture

A lyotropic system, consisting of a lecithin (DMPC) and a non-ionic surfactant (C₁₂E₅) in water was studied. The system exhibits a lamellar-to-nematic phase transition. The nematic phase appears as the temperature is decreased and only exists in a very limited temperature and concentration range, for specific lipid-to-surfactant ratios. While a lamellar phase is found at higher temperatures in both mixed and pure C₁₂E₅ systems, the transition to the nematic phase at lower temperatures coincides with a micellar phase in the pure C₁₂E₅ system. The transition appears to be driven by the strong temperature dependence of the surfactant film spontaneous curvature. The structural properties of the lamellar phase close to the lamellar-to-nematic boundary have been studied by polarised light microscopy and small-angle neutron and X-ray scattering experiments. The signature of a helical defect with Burgers vector of magnitude 2 is apparent in our data, close to the lamellar-to-nematic phase transition. The proliferation of screw dislocations in the lamellar phase might be a plausible mechanism for driving this transition. Received 6 July 1999 and Received in final form 17 April 2000     

Temperature dependence of the effective anchoring energy for a nematic-ferroelectric interface

Specific features of the anisotropic interaction between a nematic mixture and a polar surface of a ferroelectric triglycine sulfate crystal have been studied over a wide temperature range including the substrate's Curie point T_c. The mixture was composed of two nematic liquid crystals, 60% of p-methoxybenzylidene-p-n-butylaniline (MBBA) and 40% of p-ethoxybenzylidene-p-n-butylaniline (EBBA), and doped with a small amount of a dichroic dye. The temperature dependence of the polarized components of optical density D_j of the dye absorption band for the nematic and isotropic phases of the MBBA+EBBA mixture has been obtained using polarization optic techniques. The temperature-induced structural changes in the nematic layer near T_c were found to be related to the changes in the orientational part of the tensor order parameter Q_ik. The experimental data have been interpreted using the model, in which the dispersive van der Waals forces of the substrate stabilize the planar orientation of the nematic in the bulk competing with the short-range anchoring forces in the vicinity of T_c. At the same time, the anisotropic part of the surface energy has two terms with the orthogonal easy axes. The nature of the surface electric field and its effect on the director alignment at the interface have been clarified. Taking into account the known relation between anchoring strength and the nematic order parameter, the effective anchoring energy w_eff for the studied system has been determined as a function of temperature.     

Refractive index and orientational order parameter of a polar–polar binary system showing induced smectic Ad and re-entrant nematic phases

Refractive index measurements have been done on a polar–polar binary system, 4-cyanophenyl [4′(4″-n-heptylphenyl)] benzoate (7CPB)?+?4-cyanophenyl-4-nonylbenzoate (9.CN), exhibiting nematic–smectic A_d–re-entrant nematic phase sequence using thin prism technique. From refractive index as well as density data, the polarizability anisotropy in the mesomorphic state has been calculated from the standard Vuks model and the orientational order parameter (?P ₂?) values have been determined. By measuring the refractive indices and density in the solid phase, the validity of the Haller's extrapolation method for systems having higher order phases has been verified. The temperature variation of the density, birefringence, and ?P ₂? values at the nematic–smectic A_d and smectic A_d–re-entrant nematic transitions for all the mixtures are found to be continuous. The experimental ?P ₂? values have been compared with our previous X-ray data and also those calculated from the Luckhurst and Timimi model.     

A possible similarity between lyotropic cubic phases and cholesteric blue phases

Summary The common features in structures and properties of lyotropic cubic phases (LCP) and cholesteric blue phases (BP) are discussed. In both systems the cubic phases have nontrivial structures governed by frustrations. The frustration is connected with the double-twist in BPs and with the layer curvatures in LCPs. The structure of BP can be quantitatively described using the minimization of the Landau free energy with tensor order parameter. The order parameter of LCP is unknown till now; however, some minimization procedure can also be used for the solution of the phase problem. It is noted that in both systems the stable amorphous phases are observed (the fog phase or BPIII in BPs andL ₃ phase in lyotropic crystals). The importance of the observation of ?forbidden? reflections for the unequivocal identification of the space groups is emphasized. Work presented at the second USSR-Italy Bilateral Meeting on Liquid Crystals held in Moscow, September 15–21, 1988.     

Optical properties of lyotropic mesophases

Summary A brief review of early studies of optical properties of lyotropic mesophases is presented. New results about refractive-index measurements in various phases of a ternary system are shown. Emphasis is given to the optical properties of the different lyotropic nematic mesophases. Finally a short review is then devoted to the optical effects of external applied fields such as magnetic, electric and mechanical ones. Associated to the GNCL (National Discussion Group on Liquid Crystals) and supported by the GNSM of the National Research Council.     

Study on optical characterization of TGB and reentrant smectic-A phases in binary mixture of two liquid crystals

In this work, our investigation is to study the optical and thermal properties of the binary mixture of cholesteric and nematic compounds, namely, cholesteryl nonanoate and p-methoxybenzylidene-p-ethylaniline, which exhibits a very interesting liquid crystalline twisted grain boundary (TGB) phase and reentrant smectic-A phase. The chiral liquid crystalline TGB phases and reentrant smectic-A phases have been observed at different concentrations and at different temperatures. The existence of TGB and reentrant smectic-A phases is confirmed by differential scanning calorimetry and optical microscopic studies. The variation of optical anisotropy has been discussed. The helical pitch of the cholesteric phase has also been discussed.     

Orientational order and distribution function in nematic 1-(4-trans hexylcyclohexyl)-4-[(2-4-isothiocyanato phenyl)ethyl] benzene

The refractive indices (n _e,?n _o) and density have been measured as a function of temperature in the liquid-crystalline and liquid phases of nematic 1-(4-trans hexylcyclohexyl)-4-[(2-4-isothiocyanato phenyl)ethyl] benzene. The molecular polarizability and orientational order parameter have been computed using the Neugebauer anisotropic local field model. The distribution function f(β), and hence the higher order parameter ?P ₄?, and nematic pair-potential have been computed at different temperatures in the nematic phase.