Phase studies and thermal stability of binary systems of cholesteric liquid crystals

The binary mixture of cholesteryl oleyl carbonate (COC) and cholesteryl nonanoate (CN) with different ratios has been characterized by differential scanning calorimetry (DSC) to determine the phase diagrams. Their normal shelf-life and accelerated stability studies were also examined. A novel microscopic Fourier-transform infrared (FT-IR) spectrometer equipped with DSC was also used to measure simultaneously the chemical structural variation and the thermal response of these liquid crystals. The results indicate that the binary mixture might transform from smectic to cholesteric and then to isotropic liquid (CN composition <50%); from solid to cholesteric and then to isotropic liquid (CN composition >50%). Therefore, the 50% CN composition might play a critical role in the phase transition of the binary COC-CN mixture. The microscopic FT-IR/DSCsystem could also confirm the phase transition, but could measure the phase trasition temperature of liquid crystals more easily and sharply than the DSC method. The long-term accelerated thermal stability of the COC-CN mixture seemed to be more constant when stored at 4 °C than in any other temperature conditions.     

Ferroelectricity in mixtures of mesogenic and nonmesogenic compounds

It is shown that by adding potassium nitrate (1 % by weight) to compensated cholesteric mixtures (cholesteryl chloride-cholesteryl myristate 63.63:36.37% by weight and cholesteryl laurate-cholesteryl chloride 35.65% by weight) or to smectic sitosteryl undecilenate, the mixtures exhibit ferroelectric behaviour. Values of P_s = 10-⁹ - 10-⁸ C/cm² were obtained in the high-temperature range. In compensated cholesteric mixtures, the spontaneous polarisation reached a minimum at a temperature corresponding to the cholesteric-nematic transition. The results are explained by assuming coupling between the dipoles of the antiferroelectric KNO₃ and the dipoles of the mesogenic compound.     

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.     

Viscoelastic modes in chiral liquid crystals

Viscoelastic properties of liquid crystals are very important for applications like display technology. However, there are not many direct techniques to study them. In this review, we describe our studies on the viscoelastic modes of some chiral liquid crystals using dynamic light scattering. We discuss viscoelastic modes corresponding to the C director fluctuations in the chiral smectic C phase and the behaviour of the Goldstone-mode near the chiral smectic C-smectic A phase transition. In cholesteric liquid crystals, we consider the director fluctuations in a wavevector range comparable to the inverse pitch of the cholesteric. Here, the study of the scattered light in the vicinity of the Bragg reflection using a novel geometry will be presented.     

Effect of the chiral chain length on structural and phase properties of ferroelectric liquid crystals

Studies of structural and phase properties obtained on several ferroelectric liquid crystalline materials with 2-alkoxypropionate group used as a chiral centre and without any lateral substitution are presented. In dependence on the chiral chain length these compounds exhibit the cholesteric N* phase, the ferroelectric smectic C* and a low-temperature SmX phase. Values of the spontaneous polarization and spontaneous tilt angle have been determined within the whole range of the SmC* phase. A low-temperature SmX phase has been identified as the orthogonal hexatic SmB* phase. The molecular parameters, namely the layer spacing in the SmC* and SmB* phases and the average intermolecular distances (D) between neighbouring parallel molecules in all investigated phases have been determined using the results of the X-ray diffraction obtained on non-oriented samples. The effect of the chiral chain length on mesomorphic, structural and physical properties of the studied ferroelectric liquid crystalline materials is discussed.     

Texture transitions in binary mixtures of 6OBAC with compounds of its homologous series

Recently the authors have observed in compounds of the 4,n-alkyloxybenzoic acid series, with the homologous index n ranging from 6 to 9, a texture transition in the nematic range which subdivides the nematic phase in two sub-phases displaying different textures in polarised light analysis. To investigate a persistence of texture transitions in nematic phases, we prepared binary mixtures of 4,6-alkyloxybenzoic acid (6OBAC) with other members (7-, 8-, 9-, 12-, 16OBAC) of its homologous series. Binary mixtures exhibit a broadening in the temperature ranges of both smectic and nematic phases. A nematic temperature range of 75°C is observed. In the nematic phase, in spite of the microscopic disorder introduced by mixing two components, the polarised light optics analysis of the liquid crystal cells reveals a texture transition. In the case of the binary mixture of 6OBAC with 12OBAC and with 16OBAC, that is of compounds with monomers of rather different lengths, the texture transition temperature is not homogeneous in the cell, probably due to a local variation in the relative concentrations of compounds.     

Phase diagram involving the mesomorphic behavior of binary mixture of sodium oleate and orthophosphoric acid

The present investigation deals with the binary mixture of two non-mesogenic compounds, viz. sodium oleate (Naol) and orthophosphoric acid (H₃PO₄) which exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixtures with concentrations ranging from 10% to 90% Naol in H₃PO₄ exhibit SmA, SmC, SmE and SmB phases, sequentially when the specimen is cooled from its isotropic phase. Physical properties, such as ultrasonic velocity, adiabatic compressibility and molar compressibility, show anomalous behavior at the isotropic to mesosphase transition.     

Identification of a TGBA liquid crystal phase via its defects

We have shown that cholesteryl nonanoate, a thermotropic compound which is well known to exhibit pretransitional effects at the smectic A (SmA) cholesteric (N*) transition (W.L. McMillan, Phys. Rev. A 4, 1238 (1971); 6, 936 (1972)), has in fact a TGBA phase in between. Our arguments rely on the observation of new TGBA defects, either in Robinson spherulites cooled from the N* phase or in free-standing films. The same new defects can be obtained in a well-documented TGBA phase of a tolane compound. We analyze qualitatively the TGBA defects in both geometries, in particular their relation to the disclination radius of the N* Robinson spherulites. Received 12 February 2001     

Tuning the phase diagrams: the miscibility studies of multilactate liquid crystalline compounds

Design of binary and multicomponent liquid crystalline mixtures is a very powerful tool to reach the desired self-assembling properties. Beyond many advantages, this method has a distinct negativity – it is very material-consuming. While working with unique chiral materials in the research laboratory, this problem can be solved by applying miscibility study by the contact preparation method. In this work, the miscibility studies of lactic acid derivatives and non-chiral/chiral liquid crystalline molecules of different structure have been done in order to establish the phase diagrams. Special attention is focused on the ferro(antiferro)electric smectic phases.     

Microscopic vs. macroscopic origin of the Lehmann effect in cholesteric liquid crystals

In a recent letter (EPL 97, 36006 (2012)), we have shown that the Leslie thermomechanical coupling cannot alone explain the Lehmann effect (namely the rotation of cholesteric droplets when they are subjected to a temperature gradient). This result was obtained by measuring in a compensated cholesteric mixture the “Lehmann coefficient” as a function of temperature both below and at the transition to the isotropic liquid. In this article, we detail these experiments and present new ones performed with other compensated mixtures and a diluted cholesteric mixture. The new results confirm the macroscopic origin of the Lehmann effect, in contrast to the Leslie thermomechanical effect that is clearly of microscopic origin.     

Deduction of the temperature-dependent structure of the four-layer intermediate smectic phase using resonant X-ray scattering

A binary mixture of an antiferroelectric liquid-crystal material containing a selenium atom and a highly chiral dopant is investigated using resonant X-ray scattering. This mixture exhibits a remarkably wide four-layer intermediate smectic phase, the structure of which is investigated over a temperature range of 16K. Analysis of the resonant X-ray scattering data allows accurate measurement of both the helicoidal pitch and the distortion angle as a function of temperature. The former decreases rapidly as the SmC ^* phase is approached, whilst the latter remains constant over the temperature range studied at 8^°±3^° . We also observe that the senses of the helicoidal pitch and the unit cell of the repeating four-layer structure are opposite in this mixture and that there is no pitch inversion over the temperature range studied.     

Determination of phase transitions in binary systems of mesogenic compounds by optical absorption spectroscopy

The use is described of absorption spectroscopy for determining phase transitions in the mesogenic compound cholesteryl myristate (CM) and in binary mixtures of terephthalbis-butyl-aniline (TBBA) and cholesteryl myristate. The temperature dependence of the optical densities in the visible region at phase transitions is reported. The transition temperatures obtained with this method are in good agreement with the results obtained with other methods.     

Study of phase behavior in a system of linear hydrogen-bonded carboxylic acid homologues

The system of hydrogen-bonded liquid crystals formed from binary mixtures p-n-heptyloxybenzoic (I) acid and p-n-undecloxybenzoic (II) acid has been investigated by polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction, and scattering and dielectric measurements. The T–X phase diagram was obtained for this system. All mixtures show enantiotropic smectic and nematic phases. The crystalline phase represents a (α, β) solid solution. At the 2:1 ratio of I to II, an intermediate phase – co-crystal γ – is formed. The co-crystal γ possesses a much wider mesophase range than the corresponding initial components. In contrast to mixtures based on the solid solutions having a positive anisotropy, the co-crystal shows a negative dielectric anisotropy in the mesophase.     

Optical and thermal studies on viscous lamellar smectic phases in binary mixture of DTAC and ortho-phosphoric acid

The binary mixture of two non-mesogenic compounds, namely, dodecyl trimethylammonium chloride (DTAC) and ortho-phosphoric acid (H₃PO₄) exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixture with lower and higher concentrations of DTAC exhibits SmA, SmD, SmB and SmE phases, sequentially when the specimen is cooled from its isotropic phase. Different liquid crystalline phases observed in the mixture were studied using optical microscopic techniques. The temperature variations of optical anisotropy and electrical conductivity have also been discussed. Helfrich potential and elastic moduli have also been estimated in the smectic phase using the Helfrich model.     

Positron lifetimes in five phases of BEA

Positron lifetimes have been measured as a function of temperature in 4-butyloxybenzal-4′-ethylaniline (BEA). BEA has been previously reported to have two liquidcrystalline phases (smectic and nematic) with transition temperatures as follows: solid → smectic, 40.5° C; smectic → nematic, 51.0° C; and nematic → isotropic liquid, 65.5° C. Positron life time spectra were resolved into two components, with the shorter component τ₁ remaining approximately constant in all phases, and τ₂ exhibiting reversible changes at all of the above transitions. In addition, an irreversible discontinuity in the τ₂ lifetime was observed in the vicinity of 28° C, indicating the presence of a new phase (phase X) of BEA. The τ₂ andI ₂ values obtained for the various phases of BEA are: solid (1.25 nsec, 7.1%), phase X (1.97 nsec, 26.2%), smectic (2.36 nsec, 23.6%), nematic (2.72 nsec, 28.3%), and isotropic liquid (2.69 nsec, 29.8%).     

Design, synthesis and characterization of a linear hydrogen bonded homologous series

A linear hydrogen bonded liquid crystalline homologous series has been synthesized and characterized. Hydrogen bond is formed between p-n-dodecyloxy benzoic acid and various p-n-alkyl benzoic acids whose alkyl chain vary from octyl to ethyl. Synthesized complexes are characterized by FTIR, ¹H NMR and ¹³C NMR studies for inferring the formation of hydrogen bonds. Polarizing Optical Microscopy (POM) and DSC studies reveal various mesophases and their corresponding transition temperatures along with respective enthalpy values. All the seven synthesized complexes exhibit rich liquid crystalline mesomorphism. A new phase namely smectic X has been observed in five of the complexes with a narrow thermal range. This phase has been characterized by optical textural, DSC, tilt angle and helicoidal pitch studies. Smectic X is sandwiched between traditional smectic C and re-entrant smectic C (designated as C_R) phases. Homeotropic transition in nematic phase is observed in all the mesogens and thus these materials can be used as thermally controlled optical shutters. Tilt angle in smectic C, smectic X and smectic C_R phases have been experimentally elucidated for all the mesogens.     

Zigzag instability of a χ disclination line in a cholesteric liquid crystal

We studied the formation of χ disclination lines in planar cholesteric samples placed in a temperature gradient near the cholesteric to smectic A phase transition. We observed that the first simple line which forms close to the smectic-cholesteric front zigzags when it is perpendicular to the direction of planar anchoring and is straight for other orientations. This instability is similar to Herring instability for crystalline surfaces. We show numerically that it originates from a strong increase of the elastic anisotropy close to the transition. In addition, we propose a new method to measure the pitch divergence at the smectic to cholesteric phase transition.     

Ultrasonic attenuation near the cholesteric → smectic A transition

Ultrasonic attenuation at 2 MHz has been measured through the cholesteric → smectic A transition in cholestryl nonanoate. Very near the transition, 0.1 < (T ? T_c) < 0.6°C, the excess attenuation varies as (T ? T_c)ⁿ, where n for four separate runs varies between 0.30 and 0.34. These values are very close to the exponent of 0.33 predicted using a scaling laws and observed for the divergence of the twist viscosity in the nematic phase as the smectic A transition is approached.     

Dielectric and calorimetric studies on 1BC1EPOPB feroelectric liquid crystal having a large spontaneous polarization

Experimental investigations on the ferroelectric liquid crystal, R-4′(1-butoxycarbonyl-1-ethoxy) phenyl 4-(4-octyloxy phenyl) benzoate (1BC1EPOPB) of large spontaneous polarization (P _S(+) = 240?nC?cm^?2), using dielectric and calorimetric techniques, are reported. The temperature range of 25.0–125.0°C has been chosen for dielectric measurements. Dielectric dispersion studies are carried out in the temperature range 45.0–75.0°C and in the frequency range 2?Hz to 2?MHz for the smectic A, smectic C* and smectic X phases. A new phase called ‘smectic X’ has been found around 56.3°C. The transition temperatures identified by the dielectric dispersion studies for different phases and those given by DSC techniques are in close agreement.