Density studies across the smectic G-nematic and nematic-lsotropic transitions

The densities of N(p-n-pentyloxy benzylidene) p-ethylaniline and N(p-n-hexyloxy benzylidene) p-ethylaniline are measured as a function of temperature from the isotropic liquid to the smectic G phase. Both the compounds exhibit enantiotropic smectic G and nematic liquid crystalline phases. The changes in density across the phase transformations and the thermal expansion coefficient confirm the order of the transitions as of first order. The particular importance of the smectic G to nematic transformation is apparent from the density jump across the transition. An estimate of the pressure dependence of the isotropic-nematic transition temperature is found to be in reasonable accord with the literature data.     

The McMillan parameter as an effective field variable for the nematic–smectic tricritical point in NO.M compounds

The dependence of the coupling of orientational and translational order parameters on the nematic-smectic A tricritical point (TCP), observed through birefringence experiments in the pure compounds and in the binary mixtures in the homologous series of N(p-n-alkyloxybenzylidene)p-n-alkylanilines, results in a mean field tricritical exponent. The McMillan parameter, M = T _NA/T _NI (where T _NA and T _NI are the smectic A—nematic (AN) and the nematic—isotropic (NI) phase transition temperatures respectively), is used as an effective and relevant field variable in analysing the TCP. The observed linear dependence of the jump in the orientational order parameter with new density variables in the tricritical region is found to be consistent with the results obtained from both the Landau mean field and the decoupled mean field models. The width of the mean field tricritical region is discussed in terms of the McMillan parameter. Further, the McMillan parameter is observed to be characteristic of chemical composition at the NA tricritical point.     

Ultrasonic investigations of N- (p-n-pentyloxybenzylidene) p-n-butylaniline

The ultrasonic velocity in N-(p-n-pentyloxybenzylidene) p-n-butylaniline is measured as a function of temperature from the isotropic liquid phase to the smectic G phase. A mixed smectic phase (S_AG) for a temperature interval of 2°C is reported. The derived parameters such as adiabatic compressibility (β_ad). Rao number (R_n) and molar compressibility (B) are also reported.     

Optical shuttering action in nematic phase of SMHBLC: observation of a ribbon-like texture

In this study, complexes belonging to supramolecular hydrogen-bonded liquid crystal homologous series are synthesized and characterized. Hydrogen bond is formed between p-n-alkyloxy benzoic acids (nBAO, where n?=?5–11) and chlorobenzoic acid (ClBAO), respectively. The isolated homologues are characterized by various techniques such as polarizing optical microscopic (POM) studies, differential scanning calorimetry (DSC), and Fourier transform–infrared spectroscopy. Based on the POM and DSC studies, the phase diagram has been constructed and discussed. A new smectic ordering, labeled as smectic R, has been characterized, which exhibits a ribbon-like texture. This phase is observed in the complexes pertaining to the higher homologous series. Tilt angle in this phase has been experimentally deduced and the results are fitted to the power law which concurs with the mean-field theory predicted value. Optical shuttering action in the homologue has been detected in the nematic phase and the results are also discussed.     

Orientational order in three nO.m liquid crystalline compounds

Refractive index and density measurements have been carried out on three nO.m liquid crystalline compounds, namely, 4O.2, 4O.3 and 1O.10 belonging to the N-(p-n-alkoxybenzylidene)-p-n-alkylaniline series. From the data, the orientational order parameter has been estimated using Vuks and Neugebauer local field models. Furthermore, the orientational order parameter has been calculated directly from refractive index data employing the Vuks scaling factor method, Neugebauer f(B) parameter, effective geometry parameter and a method proposed by Kuczyński et al. It is observed that order parameter values estimated from different methods agree well near the nematic–isotropic transition and diverge as the nematic phase attains equilibrium. The temperature gradient of refractive indices and the nematic crossover temperatures have also been estimated for these compounds. The results obtained are compared and discussed.     

Influence of pressure on the electric-field-induced phase transitions in liquid crystals

Within the framework of Landau-de-Gennes formulation, we analyse the effect of pressure on electric-field-induced phase transitions in a liquid crystal which shows spontaneously an isotropic-smectic A transition. Inferring from the experimental pressure dependences on the layer spacing in smectic A phase, as well as the nematic-smectic A metastable temperature T^*_AN, we incorporated the pressure dependence in the free energy through (the surface energy term) and the coupling between the quadrupolar nematic ordering Q_ij and the smectic order parameter ψ. From the S-T phase diagram, we found that the stability of field-induced nematic phase increases with pressure, whereas the discontinuity of the transition decreases. Also, the region where paranematic phase transits directly to smectic A phase increases with pressure.     

Synthesis and phase transition studies on non-symmetric liquid crystal dimers: N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)-benzylidene)-4-chloroanilines

A new series of non-symmetric liquid crystal dimers N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)benzylidene)-4-chloroaniline containing benzothiazole and benzylideneimine units connected by a flexible alkyl spacer, –(CH₂) _n –, with n ranging from 4 to 12 in even parity have been prepared. All five members of this homologous series exhibit an enantiotropic nematic phase. The compounds with greater n of 8–12 exhibit both nematic and smectic phases upon cooling. A notable feature among this series is that for the member with n?=?10, the smectic–nematic transition is also present. The nematic–isotropic transition temperatures and associated entropy changes with respect to all compounds in this series exhibit a dramatic dependence on the length of the flexible spacer. A comparison of the transitional properties of this series with those of α-(4-benzylidenechloroaniline-4′-oxy)-ω-[4-(thiophene-2-carboxyl)benzylideneaniline-4′-oxy]alkanes reveals that replacing benzothiazole moiety at one side of the flexible alkyl spacer reduces the nematic–isotropic transition temperature.     

Texture transitions in the liquid crystalline alkyloxybenzoic acid 6OBAC

The 4,n-alkyloxybenzoic acid 6OBAC has a very rich variety of crystalline structures and two nematic sub-phases, characterised by different textures. It is a material belonging to a family of liquid crystals formed by hydrogen bonded molecules, the 4,n-alkyloxybenzoic acids (n indicates the homologue number). The homologues with 7?≤?n?≤?13 display both smectic C and N phases. In spite of the absence of a smectic phase, 6OBAC exhibits two sub-phases with different textures, as it happens in other materials of the homologue series which possess the smectic phase. This is the first material that exhibits a texture transition in a nematic phase directly originating from a crystal phase. Here we present the results of an image processing assisted optical investigation to characterise the textures and the transitions between textures. This processing is necessary to discriminate between crystal modifications and nematic sub-phases.     

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.     

Mechanical behavior of the smectic phases near the phase transitions

We present experimental data on the apparent layer complex rigidity of the smectic A, C, B phases of 40 P90B versus temperature at a fixed frequency of 50 Hz. Across the nematic → smectic A and smectic A → smectic C second order transitions, the modulus of the rigidity coefficient becomes very weak, and its phase undergoes a rapid variation of π, in a range of about 100 mK. At the first order smectic C → smectic $\text{B}$ transition, a corresponding discontinuity is observed. This behavior is tentatively explained in term of coupling of the nematic director (or defects) with the shear flow associated with the compression, and an associated viscoelastic relaxation.     

Phase transition studies in polymesomorphic compounds (ii): Ultrasonic velocity studies in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline

The variation of ultrasonic velocity in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline with temperature in the isotropic, nematic, S_A S_B and S_G phases is measured. All the phase transitions are of first order. The adiabatic compressibility β _ad , molar sound veclocity or Rao number R_n , and molar compressibility or Wada constant A are computed. Molar sound velocity and molar compressibility of HBBA are compared with the values of other compounds. They are found to be in good agreement with theory.     

Undulation textures at the phase transitions of some alkyloxybenzoic acids

We observed undulated smectic textures for some compounds of the 4,n-alkyloxybenzoic (nOBAC) acid series, at transitions between the smectic and the isotropic phase and between the smectic and nematic phase. Studied compounds were 12OBAC, 16OBAC and binary mixtures of 12- and 16OBAC. The undulations are dressing a usual Schlieren texture. An interesting fingerprint pattern is observed at the smectic-nematic in the case of the binary mixture, approximately 1 : 1 in weight.     

Stress anisotropy in liquid crystalline phases

Monte Carlo simulations of bulk liquid crystals in the isotropic, nematic and smectic phases were performed. The simulations were carried out using different box shapes. The diagonal components of the pressure tensor were calculated to verify that the system is in mechanical equilibrium. For simulations in cubic boxes it was found that the three components of the pressure tensor had the same values in the isotropic and nematic phases but they were different in the smectic phase, i.e. the system seemed to be under anisotropic stress. NVT and NPT simulations in the smectic phase were performed by allowing the box sides to fluctuate independently; in this case, the average diagonal components of the pressure tensor had the same value. Inaccurate calculation of the total pressure produces incorrect equilibrium boundaries in the phase diagram. Microphases and poorly defined layering can be found in simulations of smectic phases when they are performed on cubic boxes. Although the pressure anisotropy is relaxed out, the layering structure in smectic phases seems to depend on the initial configuration, regardless of the simulation method.     

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

A homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IV_n), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1–10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.     

Dielectric investigations in the nematic and hexatic smectic B phases of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

Temperature-dependent dielectric characterization of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl (HIEB), which exhibits smectic B and nematic phases, has been carried out over the frequency range of 1 Hz to 10 MHz for homeotropic and planar alignment of sample molecules. This compound shows positive dielectric anisotropy (Δε = ε _∥ ? ε _⊥ > 0) in the nematic (N) phase. One mode of dielectric relaxation showing Arrhenius behaviour has been detected in the hexatic smectic B (SmB) phase. Various electrical parameters, namely, dielectric anisotropy, relaxation frequency and activation energy, have been determined in the N and SmB phases.     

Phase transition studies in N(p-n-pentyloxy benzylidene) p-n-decyl aniline

The temperature dependences of the molar volume, the ultrasonic velocity and the refractive index in N(p-n-pentyloxy benzylidene) p-n-decyl aniline, which exhibits nematic, smectic-A and smectic-B, phases, are presented. The isotropic-nematic and smectic-A-smectic-B phase transitions are found to be of first order while the nematic-smectic-A transition is of second order. The thermal expansion coefficient (a) computed from the molar volume data agrees with a second-order N-S_A transition. The computed adiabatic compressibility β_ad, molar sound velocity (or Rao number R_n ) and molar compressibility (or Wada constant A) are presented.     

Studies on the microstructure of phase transitions in two kinds of liquid crystals by PAT and DSC

The positron lifetime and DSC measerments for EBBA and DOBAMBC have been made with heating and cooling clycles. The experimental results show that a shorter lifetime (₁) is essentially independent of temperature while the longer lifetime (₂) and the intensity (I ₂) change abruptly double or triple with temperature. Consequently, the EBBA has only nematic phases while the DOBAMBC has two liquid-crystalline phases (smectic C* and smectic A) with transition temperatures as follows: for EBBA, solid nematic (304.5 K), nematic isotropic (356.5 K), isotropic nematic (356.5 K), nematic solid (301 K); and for DOBAMBC, solid smectic C* (346 K), smectic C* smectic A (357.5 K), smectic A isotropic (389 K). These critical temperatures are in accordance with the transition temperatures measured by DSC. In addition, the difference in the solid-nematic transition temperature in the heating and cooling cycles was also observed. A discussion about the correlation of the observed changes in lifetime (₂) with the changes in molecular orientational order (S) and dielectric anisotropy () is presented.     

Orientational order parameters of a binary mixture showing both induced smectic and re-entrant nematic phases

The phase diagram of a new binary system of two polar nematic compounds, 4-cyanophenyl [4′ (4″-n-heptylphenyl)] benzoate(7CPB) and 4-cyanophenyl 4-nonylbenzoate (9.CN), shows the presence of both the induced smectic and re-entrant nematic phases in a certain concentration range 0.4 < x _9.CN < 0.87. The results of X-ray diffraction and density measurements are reported here. Orientational order parameters have been determined in the induced smectic, normal nematic and re-entrant nematic phases from X-ray diffraction measurements. The order parameters have been fitted to those calculated from modified McMillan's theory as proposed by Luckhurst and Timimi. The agreement is found to be closer to the modified model. The experimental variation of the layer thickness with mole fraction of 9.CN has also been explained fairly well by assuming the presence of two types of homo dimers (7CPB + 7CPB, 9.CN + 9.CN) and one type of hetero dimer (7CPB + 9.CN).     

Synthesis and mesomorphic behaviors of a series of heterocyclic pyridine-imine-ester based liquid crystals

ABSTRACT

A series of new calamitic liquid crystals, 4-{[(5-methylpyridin-2-yl)imino]methyl}phenyl 4-alkoxybenzoates were synthesized. This series consists of nine members wherein they are differed by the length of alkoxy chain. Spectral analysis results were in accordance with the expected structure. Their thermotropic behaviors were analyzed with Differential Scanning Calorimetry (DSC), Polarizing Optical Microscopy (POM) and powder X-ray diffraction techniques. First member with the shortest alkoxy chain (n?=?2) is a non-mesogen. As the alkoxy chain increased to n?=?4, the monotropic nematic phase appeared. An enantiotropic mesophase (nematic) was observed for the following three members (n?=?6, 8, 10). As the alkoxy chain increased to n?=?12, enantiotropic nematic phase exhibited together with monotropic smectic A (SmA) phase. As the alkoxy chain continuously increased to n?=?14 and 16, enantiotropic phases were observed for both N and SmA. When moving to n?=?18, the nematic phase disappeared and this compound only exhibited a single mesophase (SmA).     

Dielectric heating and relaxations in smectic a liquid crystals

The dependence of the temperature changes ΔT on frequency occurring in the smectic A, nematic and isotropic phase of a positive dielectric liquid crystal material initiated by dielectric heating is investigated. The same relaxation mechanism governing the strong increase of ΔT in nematics is shown to be responsible for inducing comparably strong dielectric heating effects in smectic A phases.