X-ray studies of the smectic B phase of the 4-bromobenzylidene-4′-alkoxyanilines

The results of X-ray studies of the nine members (4?÷?12) of the 4-bromobenzylidene-4′-alkyloxyaniline homologous series (nBBAA) in smectic B (SmB) and smectic A (SmA) phases are presented. Interestingly, no SmC phase was identified. The thickness of smectic layers in the SmA and SmB phases was estimated showing unexpectedly that in SmA it is bigger than in the SmB. For the SmB phase, orthorhombic unit cell parameters were determined as a function of temperature. The obtained data are discussed in relation to rotational dynamics.     

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.     

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.     

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.     

Double hydrogen bonded ferroelectric liquid crystals: A study of field induced transition (FiT)

A novel series of chiral hydrogen bonded liquid crystals have been isolated. Hydrogen bond was formed between chiral nonmesogen ingredient levo tartaric acid and mesogenic p-n-alkoxybenzoic acids. Phase diagram was constructed from the transition temperatures obtained by DSC and polarizing optical microscopic (POM) studies. Thermal and electrical properties exhibited by three complexes namely LTA+8BA, LTA+7BA and LTA+5BA were discussed. Salient feature of the present work was the observation of a reentrant smectic ordering in LTA+8BA complex designated as C_r¹ phase. This reentrant phenomenon was confirmed by DSC thermograms, optical textures of POM and temperature variation of capacitance and dielectric loss studies. Tilt angle was measured in smectic C¹ and reentrant smectic C_r¹ phases. Another interesting feature of the present investigation was the observation of a field induced transition (FiT) in the LTA+nBA homologous series. Three threshold field values were noticed which give rise to two new phases (E₁ and E₂) induced by electric field and on further enhancement of the applied field the mesogen behaves like an optical shutter. FiT is reversible in the sense that when applied field is removed the original texture was restored.     

Design,synthesis and characterization of a linear hydrogen bonded homologous series exhibiting reentrant smectic C ordering

Design, synthesis and characterization of seven linear hydrogen bonded liquid crystal complexes derived from mesogenic p–n-decyloxy benzoic acid and p–n-alkyl benzoic acids designated as 10OØn (where n varied from ethyl to octyl) are reported. FTIR studies confirm the hydrogen bond formation in all these complexes. The phase transition temperatures and their corresponding enthalpy values are experimentally deduced from Differential Scanning Calorimetry (DSC) studies. POM and DSC data are further utilized for the construction of 10OØn phase diagram. Two Odd–even effects have been evinced, one in enthalpy values and the other in corresponding transition temperatures across the isotropic to nematic phase transition. An interesting result is the observation of re-entrant smectic ordering, designated as smectic C_R in three higher ordered mesogens. A new smectic ordering, smectic X, has been observed which is sandwiched between traditional smectic C and re-entrant smectic C_R. Magnitudes of optical tilt angle in smectic C, smectic X and smectic C_R are experimentally found to attain saturation with decrement of temperature in the corresponding phase. The occurrence of smectic X and smectic C_R are discussed with relation to the molecular chemical structure. The optical filtering action in smectic C and re-entrant smectic C_R phases have been analyzed.     

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.     

Change of thermotropic properties in liquid crystal with multiple phase transitions: Surface “aging” effect

The effect of surface “aging” on thermotropic properties of polymorphic mesogen, 4-butoxyphenylester of 4-decyloxybenzoic acid (BPEDBA) which exhibits the smectic G, smectic C, smectic A, and nematic mesophases has been investigated. Temperatures of direct and reverse phase transitions and temperature widths of the heterophase regions have been determined with high accuracy. The shift of the phase transition temperatures and change of the temperature widths of the heterophase regions under the influence of surface “aging” have been reported.     

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.     

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.     

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%).     

Translational order parameter in the smectic-B phase of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

4-Hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1-1′-biphenyl, a liquid crystalline material shows smectic-B (SmB) and nematic phases, respectively, between 60.3–98.5°C and 98.5–130.8°C. X-ray diffraction patterns were recorded at different temperatures in the SmB phase and were used to compute translational order parameters. For this purpose, we have employed a theoretical model recently reported by Kapernaum and Giesselmann. The results obtained are discussed in terms of the basic understanding of the SmB phase.     

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.     

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).     

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.     

New investigation on the tetragonal liquid-crystalline phase or SmQ

Chiral liquid crystals, for which twist and smectic order strongly compete, can exhibit complex architectures. This is the case of the SmQ phase which shows a high degree of 3D order (tetragonal or hexagonal) as well as a liquid signature. We have combined X-ray scattering and optical observations on a new compound exhibiting a SmQ phase to discriminate between the two models proposed by A.M. Levelut et al. (J. Phys. II 7, 981 (1997)) at the molecular level for the phase with the I4₁22 space group.Received: 9 March 2004, Published online: 10 November 2004PACS: 61.30.Eb Experimental determinations of smectic, nematic, cholesteric, and other structures - 61.30.Mp Blue phases and other defect-phases     

Phase transitions and structural studies ofp-n-alkoxybenzyliden-p’-fluoro-anilines

Summary The transition temperatures and phase diagrams of five fluorinated benzylidenaniline derivatives have been studied by TM and X-ray diffraction techniques. A smectic polimorphism appears in all compounds. The structure of smecticB phases has been deeply studied in order to evidence a possible utilization of such phases as solvents able to exert stereochemical effects on polimerization reactions. The parameters of theS _B hexagonal lattice area=b=4.29 ? in all the studied compounds, whilstc varies from 18.9? to 24? as a function of the C atom number of the alkyl chain; its averaged increase is 1.265? for each CH₂ group. In any case, the distance between the smectic planes is equal to the molecular length so that interdigitated structures are to be excluded. Work presented at the First USSR-Italy Bilateral Meeting on Liquid Crystals held in Portonovo, Ancona (Italy), September 30-October 2, 1987.     

Biased motion about the long molecular axis in ‘ordered’ smectic phases as studied by deuterium NMR relaxation

Spectral densities of motion were determined by deuteron NMR relaxation measurements in the ‘ordered’ smectic-B and -G phases of 4-n-pentyloxybenzylidene-d ₁-4′-heptylaniline and 4-n-pentyloxybenzylidene-4′-heptylaniline-2,3,5,6-d ₄ at two different Larmor frequencies. Different forms of motional behaviour are involved in these phases in comparison with those in the high temperature ‘disordered’ phases. Specifically, internal ring rotation and direction fluctuation are not effective in the ordered smectic phases. In addition, the fast rotation of the molecule about its long molecular axis is now strongly hindered to give a libration motion of angular amplitudes of about 100°. The third-rate model is again used to describe the molecular reorientation, taking the restricted γ motion into account. The effects of phase biaxiality on spin relaxation in the smectic-G phase are also discussed.     

Incommensurability and metastability problems in NH4HSeO4 and ND4DSeO4: A reinvestigation of phase diagrams

Abstract

X-ray and neutron diffraction results on NH₄HSeO₄ and ND₄DSeO₄ are reported. Direct evidence of an incommensurate phase sandwiched between the monoclinic high-temperature phase (space group B2) and the low-temperature ferroelectric lock-in phase k = ? (space group P1) has been obtained in NH₄HSeO₄. The phase situation is more complicated in ND₄DSeO₄, where an incommensurate phase is found sandwiched between the B2 phase and a lock-in phase k = ¼ and where a phase in which several modulations coexist has been discovered in between the two lock-in phases k = ¼ and k = ?. The non-equilibrium processes, also present in ND₄DSeO₄, have been identified. All these results have clarified the situation about the phase diagram.     

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.