Kerr Effect Studies in Liquid Crystalline Substances

The static and dynamic pretransitional behaviour was investigated by the electric Kerr effect in three nematic substances above the clearing point. The measured Kerr constants exceed that of nitrobenzene by more than a factor of 50…︁ 80 which are due mainly to pretransition phenomena and the strong dipole moments of the compounds. A formula is given for the calculation of the Kerr constant. The latent heat at the nematic-isotropic phase transition calculated from the temperature dependence of the Kerr constant by means of the Landau theory is in good agreement with the experimental values. Size and relaxation behaviour of pseudonematic domains are determined by Kerr effect measurements.     

Ultrasonic relaxation studies in the liquid crystal 80CB

The variation of the ultrasonic velocity with temperature in the liquid crystal 4′-n-octyloxy-4-cyanobiphenyl (80CB) at four different fixed ultrasonic frequencies is studied. From these studies various relaxation parameters like the adiabatic relaxation time, velocity at zero frequency, in the vicinity of isotropic-nematic phase transition and velocity at infinite frequency are estimated. From these parameters the relaxation mechanism in the vicinity of isotropic-nematic phase transition is studied and the results are discussed.     

Dielectric Relaxation in Low Temperature Smectic Phases of 4-n-Alkyloxy-benzylidene-amino-4′-cyanobiphenyls

The dielectric behaviour of five homologous 4-n-alkyloxy-benzylidene-amino-4′-cyanobiphenyls was investigated. Especially, we were interested in the dielectric relaxation frequencies of the smectic low temperature phases S_B and S_E as well as the dielectric behaviour in the solid state. We have found in all liquid crystalline phases a low frequency relaxation region explained by a hindered rotation of the molecules around their short axes. By supercooling of the hexyl and heptyl derivatives a new liquid crystalline phase can be obtained. A dielectric relaxation in the solid phase could not be found.     

Ultrasonic relaxation studies across N-I transition in the liquid crystal p-cyanophenyl trans-4-pentyl cyclohexane carboxylate

The variation of ultrasonic velocity with temperature in the liquid crystal p-cyanophenyl trans-4-pentyl cyclohexane carboxylate at four different fixed frequencies is studied. From the observed data relaxation parameters like adiabatic relaxation time, velocity at infinite frequency and velocity at zero frequency, in the vicinity of isotropic-nematic transition are sutied. The relaxation mechanism is discussed.     

Dielectric behaviour of the smectic I phase

The dielectric behaviour of 4-n-butyl-4′-n-dodecyloxyazobenzene was investigated in the smectic A, C and I phases from 10² to 3 ṁ 10⁶ Hz. In all phases a dielectric relaxation process could be found which is connected with the reorientation of the molecules around their short molecular axes. At the phase transition S_C/S_I a step of one decade was observed in the relaxation frequencies.     

Measurements of dc Kerr Constants for a Homologous Series of Nematic Compounds

The dc Kerr constants of seven p,p′-n-alkoxyazoxybenzene homologous compounds have been measured as functions of temperature in the isotropic phase. The observed pretransitional behavior near the isotropic-nematic transition is consistent with the phenomenological model of Landau-de Gennes with the Onsager's loal-field correction included in the dielectric tensor. The dc polarizability anisotropy and the average orientation of the permanent dipole with respect to the long molecular axis are deduced from the experimental results. Their variations with increase of methylene groups in the alkyl chains are discussed.     

Investigation of the Cholesteryl Oleate Mesophases by X-Ray Diffraction

The following phase transitions occurring in the cholesteryl oleate were investigated by X-ray diffraction: solid-isotropic liquid, isotropic liquid-cholesteric, cholesteric-smectic.

The sample purity was 98%. Strong pretransitional effects were observed at the solid-isotropic liquid phase transition and at the cholesteric-smectic phase transition.

At this last transition the longitudinal coherence length ξ_∥ appears to diverge as the critical temperature is approached in the cholesteric phase, whereas the transversal coherence length ξ_τ increases at the critical temperature in the smectic phase in an abrupt way. It seems from the temperature dependence analysis of the angular position of the low angle peak that the smectic phase is a smectic A phase and that a progressive melting of chains occurs at the temperature increases.     

The influence of the boundary conditions on the character of the phase transition nematic-smectic C

The possibility is investigated for inducing the intermediate smectic A structure in substances with nematic and smectic C phases by the boundary forces. Different geometries are used: homeotropic, homogeneous and tilted under a different angle toward the supporting substrates of the liquid crystal cell. At homeotropic and at tilted orientation where the molecules tilt toward the supporting substrates is different from the molecule tilt in the smectic layer, an intermediate smectic A structure is observed at the transition nematicsmectic C in a narrow temperature interval. In this case the phase transition nematicsmectic C extends and transforms into phase transition of second order. At homogeneous orientation and at tilted orientation of an angle equal to the molecule tilt in the smectic layer, the transition nematic-smetic C carried out in two stages, as partially it begins on the surface still in the nematic phase and terminates at the temperature of the phase transition N-Sc. The influence of the boundary forces depends essentially on the energy of the phase transition N-S_C of the substances.     

Density Studies in Terephthalylidene-bis-p-n-dodecylaniline

The temperature dependence of density in Terephthalylidene-bis-p-n-dodecylaniline (TBAA12) is carried out to investigate the phase transitions, associated volume jumps, order of the transitions and to estimate the pressure dependence of transition temperatures and pretransitional effects. The compound exhibits smectic C, smectic I, smectic F and smectic G phases. The isotropic-smectic C and smectic C-smectic I transitions are found to be first order from the density jumps and the calculated thermal expansion coefficient data also supported the density results. The smectic I-smectic F transition is detectable by a change of slope in density studies, which is a second order transition inferred from thermal expansion coefficient variation with temperature.     

Coefficient of volume expansion and thermoacoustic parameters in N-(P-hexyloxybenzylidene)-P-toluidine

The Sharma constant S_o, the isochoric temperature coefficient of volume expansivity, the isochoric temperature coefficient of internal pressure, the reduced compressibility, the reduced volume and a few other acoustic parameters are evaluated for N-(P-Hexyloxybenzylidene)-P-Toluidine (HBT) using only the coefficient of volume expansion. The Sharma constant which was shown by Sharma to be a constant in a number of non-mesomorphic systems is bound to be a constant in the liquid crystal HBT also, investigated by the authors with the same character constant value both in the isotropic and nematic phases with anomalous behaviour and pretransitional effects at and in the immediate vicinity of the isotropic-nematic phase transition temperature. The various other acoustic parameters estimated for liquid crystal HBT investigated in the present studies are compared and discussed with the values reported by Sharma, and by Sharma and Reddy for certain other non-mesomorphic systems.     

The Dielectric Anomaly Near the Transition from the Smectic A* to Smectic C* Phase and Visco-Elastic Properties of Ferroelectric Liquid Crystals

A pyro-electric technique is developed which allows the measurement of the dielectric response near the A*-C* phase transition in ferroelectric liquid crystals. The temperature dependence of the elastic modulus K _θ(T) corresponding to the molecular tilt in smectic layers is calculated from the experimental data. Direct pyro-electric measurements of the relaxation time for the spontaneous polarization P _s and the data on K _θ(T) allow us to calculate the temperature behaviour of the twist-viscosity γ₁(T) for the smectic C* phase. The curves γ₁(T) are compared for the smectic C* and the nematic phase of the same compound and the dependence of the twist viscosity on the molecular tilt angle in the C* phase is investigated. The results of the dielectic measurements are discussed in terms of the mean-field approximation.     

The Order-Disorder Phase Transition in Liquid Crystals as a Function of Molecular Structure. I. The Alkyl Cyanobiphenyls

The pretransitional behaviour of a homologous series of mesomorphic compounds, the alkyl cyanobiphenyls (CNρρC _n H _{2n + 1}) for n = 5–12, has been studied as a function of temperature by light scattering in the isotropic phase. The higher homologues, n = 8–12, exhibit a smectic A phase that becomes increasingly important at the expense of the nematic phase for increasing n and for n = 10 and 12 no nematic phase is observed. We have shown from light scattering and differential scanning calorimetry measurements that the presence of the smectic A phase changes markedly the pretransitional behaviour, and gives rise to two distinct pretransitional regions. The first region is for temperatures greater than ～3°C above the clearing temperature T_c where the systems exhibit a typical pretransitional behaviour adequately described by the phenomenological Landau-de Gennes model of a second order phase transition with an intervering first order transition at T_c . The constants of this model for this region are given and show a distinct odd-even effect. The second region is close to T_c where a strong divergence from the already critical behaviour is observed. This secondary divergence is observed to be a function of the alkyl chain length and its conformation, and is attributed to coupling between smectic A like layers and the orientational order parameter in the isotropic phase.     

Pressure Study of a Hexatic B and Crystal B Phase

Pressure temperature phase diagrams of two compounds exhibiting smectic B phases are presented. In one compound, the smectic B phase is liquid (no long range positional correlations) and is called a hexatic B phase, whereas in the other the smectic B phase is crystalline in nature. “Transition bars”, which are often observed at a smectic A to crystal B transition are observed above 1.5 kbar (and not below) in the former compound and the smectic A phase appears quite piezo-resistant. In contrast, for the latter compound, the smectic A phase disappears above 1.94 kbars. These results suggest that the two smectic phases are stabilized by different forces and we suggest a model.     

The Smectic A-Smectic A Transition in a Homologous Series of 4-(4-Alkoxyphenoxycarbonyl)phenyl 5-Cyano-2-furancarboxylates

The thermal properties for a homologous series of 4-(4-alkoxyphenoxycarbonyl)phenyl 5-cyano-2-furancarboxylates have been examined. The smectic A phase commences from the hexyloxy homolog, and the octyloxy, nonyloxy and decyloxy homologs show two kinds of smectic A phases and experience the S_A-S_A transition. The lower phase which shows a typical fan shaped texture is assigned to a smectic A with a bilayer arrangement of the molecules (S_A2). The higher phase which shows a typical fan shaped texture on the cooling stage and a broken fan one on the heating stage, is assigned to a smectic A with a partially bilayer arrangement of the molecules (S_Ad). The S_A-S_A transitions could be easily detected by both differential scanning calorimeter and optical microscopic method.     

High Frequency Dielectric Relaxation of a Ferroelectric Liquid Crystal

Dielectric relaxation measurements on a optically active thiadiazole derivative in the frequency range from 1 MHz to 1 GHz gave relaxation frequencies between 100 MHz and 1 GHz in the smectic C* phase. This relaxation which is related to molecular reorientation processes around the long molecular axis is connected with a mean activation energy of 57 kJmol⁻¹. A simple model of the energetic behaviour of this reorientation including the production of the spontaneous polarization is discussed.     

Phase transition studies in mesogenic dimers

Schiff base liquid crystal dimers, both symmetric and non‐symmetric, in which two anisotropic groups are linked by a flexible spacer, exhibit a rich variety of smectic mesomorphism. The interest in this class of mesogens stems not only from their ability to act as model compounds for semi‐flexible mainchain liquid crystal polymers but also from their quite different properties compared to conventional low molar mass liquid crystals (monomers). We report here the phase transition studies on two examples of these schiff base liquid crystal dimers using the Differential Scanning Calorimetry and density measurements as a function of temperature. The symmetric liquid crystal dimer, α,ω‐bis (4‐n‐dodecylaniline benzylidene‐4′‐oxy)decane (10.O12O.10) exhibits a very rare Isotropic to G transition. Where as, the non‐symmetric dimer, α‐(4‐cyano biphenyl‐4′‐yloxy)‐ω‐(4‐n‐decylanilinebenzylidene‐4′‐oxy)decane (CB.O10O.10) exhibits a rare nematic to intercalated smectic A phase transition. The transitions studied, isotropic to nematic and isotropic to G exhibit a large density jump at the transition confirming their first order nature. Nematic to intercalated smectic A transition is found to be a second order transition whose behavior is similar to nematic to smectic A transition. Calculated values of pressure dependence of transition temperature and thermal expansion coefficient are also reported.     

Azo benzene derivatives

Pressure-volume isotherms for 4-(trans-4-butylcylohexyl)benzonitrile were measured by means of piston-cylinder method. This substance has a monotropic nematic phase at atmospheric pressure. But over a pressure, the nature of isotropic to nematic phase transition changed from monotropic to enantiotropic phase transition. It is the first observation in P-V-T experiments that the monotropic isotropic-nematic transition changes enantiotropic under pressure.     

Phase transition behavior and structure of the thermotropic liquid crystal 6‐{[(4′‐{[(undecyl)carbonyl]oxy}biphenyl‐4yl)carbonyl]oxy}‐1‐hexyne

The phase transition behaviors and corresponding structures of 6‐{[(4′‐{[(undecyl)carbonyl]oxy}biphenyl‐4yl)carbonyl]oxy}‐1‐hexyne (A4EE11) were investigated using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X‐ray diffraction (WAXD). In comparison with the published homologues, 5‐{[(4′‐heptoxy‐biphenyl‐4‐yl)carbonyl]oxy}‐1‐pentyne (A3EO7) which shows a monotropic smectic A (SmA) phase and a metastable monotropic smectic C (SmC) phase; 5‐{[(4′‐heptoxy‐biphenyl‐4‐yl)oxy]carbonyl}‐ 1‐pentyne (A3E'O7) that exhibits three enantiotropic stable liquid crystalline (LC) phases, SmA phase, SmC phase and smectic X (SmX) phase; 5‐{[(4′‐heptoxy‐biphenyl‐4‐yl)carbonyl]oxy}‐1‐undecyne (A9EO7) which has a monotropic SmA phase and a metastable crystal phase, A4EE11 integrates the enantiotropy, monotropy and metastability of the LC phases of those three compounds. Upon cooling from isotropic state to room temperature, in the temperature range of 62.0 to 58.5°C, A4EE11 shows an enantiotropic smectic A (SmA) phase with a layer spacing d=32.69Å. Further lowering the temperature, it enters into a metastable monotropic smectic B (SmB) phase with a longer layer spacing d=34.22Å which has a tendency towards crystallization. The metastability of the liquid crystalline phase may associate to the linkage order of the ester bridge between the mesogenic core and the flexible spacer. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic Field Dependence of Laser Light Scattering through CBOOA in Nematic Phase

In the nematic phase of homeotropically aligned liquid crystals which have the smectic A phase at lower temperature, interference rings have been observed above some threshold magnetic field H_c which nearly coincides with the ocurrence of Freedericksz transition, only for the light polarized parallel to the direction of magnetic field. This interference ring disappears with increasing magnetic field above second threshold H_s . The origin of these interference rings is explained tentatively by a periodic deformation of bulk directors.

The bend elastic constant of CBOOA estimated from the measurements of the interference ring as a function of temperature, diverges with the critical exponent (0.5 ± 0.02) near the smectic A-nematic transition temperature and agrees well with a recent suggestion of McMillan based on the mean field theory.