Thermodynamic,optical and switching parameters of a ferroelectric liquid crystalline material having SmA*-SmC*-SmBh* phase sequence

Thermodynamic and electro-optical characterization of a ferroelectric liquid crystalline material, namely ((S) (+) 4-(1-methylheptyloxy) phenyl 4′-octyloxybiphenyl-4-carboxylate) possessing paraelectric SmA*, ferroelectric SmC*, hexatic SmB_h* and SmI* phases has been carried out. Phase identification has been done by optical and thermodynamic studies. Switching parameters viz. spontaneous polarization, switching time and rotational viscosity have been determined. The spontaneous polarization has been found to increase with decreasing temperature in SmC* phase. The switching time is found of the order of few milliseconds.     

Distortion and unwinding of the helical structure in polymer-stabilized short-pitch ferroelectric liquid crystal

We report the effect of an anisotropic polymer network formed from an achiral photoreactive monomer in a short-pitch chiral SmC* phase on the distortion and the unwinding of the helical structure of the ferroelectric phase. The electro-optical behaviour and ferroelectric properties were experimentally determined for films containing various polymer concentrations. The critical field, E_u, for the transition from the distorted structure to the homogeneous state was measured as a function of polymer concentration. A linear increase of E_u versus polymer concentration was observed, showing that the helical structure of the short-pitch SmC* phase was stabilized by the polymer network. This behaviour was expected to be a consequence of the increase of the apparent elastic constants of the ferroelectric liquid crystal stabilized by the anisotropic polymer network films. The polymer network morphology was investigated using atomic-force microscopy, revealing a twisted structure of the polymer fibers. This twisted structure was transferred onto a polymer network during the polymerization process within a short-pitch SmC* phase. The increase of the apparent elasticity can then be interpreted by a strong interaction between polymer network and the liquid-crystal molecules. From our experimental data, the coupling coefficient, W_p, characterizing this interaction was evaluated for all studied polymer concentrations.     

Self-assembling properties of lactic acid derivative with several ester linkages in the molecular core

The effect of several polar ester linkage groups incorporated in the molecular core of a chiral lactic acid derivative on self-assembling properties has been investigated by polarizing optical microscopy, small angle X-ray diffraction, differential scanning calorimetry, optical and electro--optical studies. The compound possesses the paraelectric smectic A* (SmA*) and ferroelectric smectic C* (SmC*) phases over a broad temperature range. Mesomorphic behaviour, spontaneous polarization, birefringence, optical transmission, dielectric anisotropy and structural properties of the self-assembled chiral material have been determined. The obtained results are discussed and compared with that of other liquid crystalline materials. Experimentally determined spontaneous polarization and tilt angle values are also used to elucidate the nature of SmC* to SmA* phase transition. The effect of polar ester linkages in the molecular core has also been discussed.     

Observation of relaxation modes in room temperature ferroelectric liquid crystal mixtures

The dielectric measurements in SmC* and SmA phases of a room temperature ferroelectric liquid crystal mixture FLC-6980 in the cells of different thickness in planer alignment have been carried out in the frequency range 100 Hz to 1 MHz. A relaxation mode (called NRM) whose dielectric increment is less than the Goldstone mode has been observed in the SmC* phase. This mode appears due to the surface effect. Goldstone mode and the soft mode was observable in the vicinity of SmC*-SmA transition temperature (T _C*A). The dielectric parameters of the Goldstone mode, new mode and the soft mode have been studied as a function of frequency and temperature. The calculated values for f_NRM, δε^NRM and distribution parameter α_NRM are found to be 325 kHz, 6 and 0.156 for 5μm thick planer cell at 37°C. It is seen that in the vicinity of theT _C*A, soft mode obeys the Curie-Weiss law given by mean field theory. The results have been compared with materials of large spontaneous polarization.     

Structural, electro-optical and dielectric characterizations of ferroelectric liquid crystals showing the SmC*–SmA*–N* phase sequence

Structural (helical pitch), electro-optical (tilt angle, spontaneous polarization and response time) and dielectric (Goldstone mode) characterizations have been performed on two pure ferroelectric liquid crystals of a biphenyl alkyloxy benzoate series and they show the N*–SmA*–SmC* phase sequence. The different results are discussed: the helical pitch, the spontaneous polarization and the rotational viscosity which is determined as a function of temperature by two methods using electro-optical or dielectric measurements. An Arrhenius behaviour of the rotational viscosity is found for the two compounds. The corresponding activation energies are determined.     

Electro-optic and dielectric studies of silica nanoparticle doped ferroelectric liquid crystal in SmC* phase

We present the results based on the electro-optic and dielectric properties of silica nanoparticle (SNP) doped ferroelectric liquid crystal (FLC) in SmC* phase. Switching time, spontaneous polarization and rotational viscosity decreases with increase in the silica concentration. An improvement in switching time after doping the silica nanoparticle is due to enhancement in anchoring energy exist between silica nanoparticle and ferroelectric liquid crystal. We noticed that the dielectric permittivity and dielectric strength decreases with increasing the concentration of silica nanoparticle in SmC* phase. Relaxation frequency increases with increasing the silica concentration and temperature in SmC* and decreases as we approaches towards transition temperature.     

Dielectric relaxation spectroscopy of guest-host ferroelectric liquid crystals: influence of anthraquinone dye

The dielectric spectroscopy of a short pitch and high spontaneous polarization ferroelectric liquid crystal mixture and its guest-host derivatives with different wt/wt ratio of anthraquinone blue dichroic dye has been studied over a wide frequency range of 50 Hz-1 MHz. The increase in dye concentration results in the decrease of the permittivity of the material in the SmC* phase, however, an opposite effect is observed in the SmA phase. The influence of bias voltage on the dielectric parameters has also been investigated. A new relaxation mode has been observed with a relaxation frequency of ∼300 kHz and dielectric strength of ∼5 at room temperature.     

Chain dynamics in a chiral C phase by deuteron spin relaxation study

Molecular reorientations and internal conformational transitions of an aligned chiral liquid crystal (LC) 10B1M7 are studied by means of deuterium spin-lattice relaxation in its smectic A (SmA) and smectic C* (SmC*) phase. The motional model which is applicable to uniaxial phases of many LCs is found to be adequate even when the phase is a tilted SmC* phase. The deuterium NMR spectrum in this phase cannot discern rotations of the molecular director about the pitch axis. The basic assumption is that the phase biaxiality is practically unobservable. However, the relaxation rates can be accounted for by the tilt angle between the molecular director and the layer normal in the SmC* phase. The tumbling motion appears to show a higher activation energy upon entering from the uniaxial SmA into the SmC* phase.     

Effect of multi-walled carbon nanotubes on dielectric and electro-optic properties of a high tilt antiferroelectric liquid crystal

By dispersing a small amount of multi-walled carbon nanotubes in a high tilt antiferroelectric liquid crystal, a nano composite is prepared. Though the phase sequence remains the same, the transition temperatures of the composite get changed, the stability of SmA* and SmC* phases increases whereas that of SmC_A* phase decreases. Pitch of the helicoidal structure shows a discontinuous change at SmC*–SmC_A* transition. Absorption strength and critical frequency of the anti-phase antiferroelectric mode are reduced in the composite. The dielectric increment of the Goldstone mode (GM) decreases and the critical frequency increases due to increased elasticity of the composite. A two-fold increase in the critical field for suppression of the GM is observed which signifies more stable helical structure in the composite. The switching time is reduced by 56% in the nano composite as a result of decrease in rotational viscosity but the high tilt remains intact. An observed lower value of conductivity indicates ion trapping in the composite.     

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     

Characteristic dielectric parameters of para-, ferro- and antiferro-electric phases of (S)-4-(1-methylheptyloxycarbonyl)phenyl-4′-(6-pentanoyloxyhex-1-oxy)biphenyl-4-carboxylate

Frequency and temperature dependence of dielectric parameters of a liquid crystalline compound (S)-4-(1-methylheptyloxycarbonyl)phenyl-4′-(6-pentanoyloxyhex-1-oxy)biphenyl-4-carboxylate under planar orientation of the molecules have been investigated in the frequency range 1 Hz-10 MHz. This compound possesses smectic paraelectric (SmA*), ferroelectric (SmC*) and antiferroelectric (SmC_A*) phases. Dielectric spectroscopy suggests the existence of a relaxation mechanism in the SmA* phase, which behaves as a soft mode. In the SmC* phase two relaxation modes are observed. One mode continues from the SmA* phase with decreasing dielectric strength and the other has characteristics of the Goldstone mode. Two dielectric relaxation modes have been observed for the SmC_A* phase. These two modes are related to the antiferroelectric ordering and the helical structure of the SmC_A* phase.     

Frustration between syn- and anticlinicity in mixtures of chiral and non-chiral tilted smectic-C-type liquid crystals

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmC a* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmC a*, transition via the SmC_β* and SmC_γ* subphases, or by “escaping” the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmC a* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality --although necessary-- does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order.     

‘Guest–host’ effect in liquid crystal mixtures

The most important goal of our research is to show the influence of the ‘guest’ (bent-core mesogen, 1,3-phenyldicarboxylatebis{4-[(4-octylbenzoyl)sulphanyl]phenyl} [IFOS8], banana-shaped liquid crystal [BLC]) on the ‘host’ (calamitic liquid crystal [CLC], (S)-(+)-1-methylheptyloxybiphenyl-(4-n-octylphenyl)thiobenzoate [MHOBS8]), on the stability and the destabilization of the antiferroelectric B2 and the ferroelectric smectic C* (SmC*) phases, and change of the temperature ranges of other phases in the binary liquid crystal mixtures. This work is focused on polymorphism of three new binary liquid crystal mixtures, exhibiting a ‘guest–host’ (guest liquid crystal–host liquid crystal [GH-LC]) effect. MHOBS8 has, among others, a ferroelectric SmC* phase, and IFOS8 assumes the B2 phase with antiferroelectric properties. The observed properties of the mixtures, such as variation of the phase transition temperatures, spontaneous polarization, tilt angle and switching time, are characteristic of a ‘guest–host’ mixture. The influence of BLC on the character of the interactions within the CLC host is discussed, with particular attention paid to electro-optical properties of the GH-LC mixtures.     

Dielectric properties of LC mixture with induced antiferroelectric phase

Mixture of two liquid crystalline components exhibits the antiferroelectric phase in a broad temperature range at room temperatures, though the two components separately do not show an antiferroelectric phase in a temperature range applied. The dielectric spectroscopy technique combined with measurements of the selective light reflection was used for identification and characterization of the phases and subphases existing in the mixture. In the SmC*_A phase, the low frequency mode characteristic of antiferroelectric phase has been detected. In the broad temperature range between SmC*_A and SmA* phases, no relaxation mode has been detected. The soft mode registered near the phase transition to SmA* phase follows the Curie-Weiss law.     

From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: A major route followed in polymer crystallization?

Based on broad and detailed evidence from a large variety of experiments on several polymer systems carried out by other authors and ourselves, a novel concept for understanding the crystallization of polymers from the melt is developed. The experiments generally indicate that the formation and growth of the lamellar crystallites is a multi-step process passing over intermediate states. We suggest a specific route which is compatible with the observations. It is proposed that the initial step is always the creation of a mesomorphic layer which spontaneously thickens, up to a critical value, where it solidifies through a cooperative structural transition. The transition produces a granular crystalline layer, which transforms in the last step into homogeneous lamellar crystallites. The model leads to predictions about the temperature dependencies of the crystal thickness and the growth rate which are at variance with conventional views but in agreement with findings in recent experiments. Received 17 February 2000 and Received in final form 30 March 2000     

A self-consistent approach for the SmA–SmC* phase transition

By using an analogy with the Maier–Saupe theory of the nematic phase, a mean field theory of the chiral smectic-C (SmC*) phase is constructed. As an order parameter of the SmC* phase, the tilt angle θ is selected, and the feedback effect of θ is introduced into the hindered rotational potential about the molecular long axis. By solving the self-consistent equation for the order parameter θ, the second-order phase transition appears. Also, to describe the SmA–SmC* phase transition under an electric field, a coupling term between a molecular dipole moment and an external electric field is introduced to the potential function. The electroclinic effect in the SmA phase and the hysteresis effect in the SmC* phase, which were described phenomenologically in the past, are found directly from the microscopic theory.     

Stripe patterns in the magnetic reorientation of a glass-forming nematic liquid crystal

We study spontaneous pattern formation in a glass-forming nematic liquid crystal during the magnetically induced dynamic Fréedericksz transition. Pattern growth rates and wavelengths as functions of the magnetic field are extracted from optical transmission textures of thin planar cells. The characteristics of the observed stripe pattern can be related to viscoelastic parameters of the nematic by means of a linear stability analysis of director fluctuation modes. The viscous properties of the material allow to vary the time scales of the experiment with temperature by orders of magnitude, leaving the spatial structure of the pattern essentially unchanged. We find that the ratios of shear and rotational viscosity coefficients relevant for the pattern wavelength selection remain constant in the temperature range investigated, whereas their absolute values change by almost two orders. Received 23 November 2001 and Received in final form 19 April 2002     

Surface and flexoelectric polarization in a nematic liquid crystal 5CB

The temperature dependence of the surface polarization has been measured for both the planar and homeotropic orientation of a nematic liquid crystal at a solid substrate. A conventional liquid crystal 5CB, pure and doped with an azo-dye, was used in cells with controlled asymmetry for light absorption. The measurements have been made by a pyroelectric technique using short pulses of a YAG laser to create a temperature increment. The latter, in turn, was measured independently by a novel time-resolved “optical thermometer” technique monitoring temperature-dependent birefringence by a He- Ne laser beam. In accordance with the symmetry of the order parameter, the surface polarization has different sign for the two orientations, its magnitude ranges from -4 to +2pC/m. The same technique has been used for the measurement of the flexoelectric polarization in hybrid cells. The sum of the flexoelectric coefficients is e ₁ + e ₃ = - 13pC/m at 25°C. Received 28 February 2000 and Received in final form 5 September 2000     

Nematic order-disorder state transition in a liquid crystal analogue formed by oriented and migrating amoeboid cells

In cell culture, liquid crystal analogues are formed by elongated, migrating, and interacting amoeboid cells. An apolar nematic liquid crystal analogue is formed by different cell types like human melanocytes (=pigment cells of the skin), human fibroblasts (=connective tissue cells), human osteoblasts (=bone cells), human adipocytes (=fat cells), etc. The nematic analogue is quite well described by i) a stochastic machine equation responsible for cell orientation and ii) a self-organized extracellular guiding signal, E₂, which is proportional to the orientational order parameter as well as to the cell density. The investigations were mainly made with melanocytes. The transition to an isotropic state analogue can be accomplished either by changing the strength of interaction (e.g. variation of the cell density) or by influencing the cellular machinery by an externally applied signal: i) An isotropic gaseous state analogue is observed at low cell density (melanocytes/mm^2) and a nematic liquid crystal state analogue at higher cell density. ii) The nematic state analogue disappears if the bipolar shaped melanocytes are forced to become a star-like shape (induced by colchicine or staurosporine). The analogy between nematic liquid crystal state analogue formed by elongated, migrating and interacting cells and the nematic liquid crystal phase formed by interacting elongated molecules is discussed. Received 2 August 1999 and Received in final form 5 January 2000     

Nonlinear dielectric response of antiferroelectric liquid crystals in the smectic Cα * phase

Nonlinear dielectric response of antiferroelectric liquid crystals has been studied in the smectic C_α* (SmC_α*) phase. The linear dielectric spectrum shows a single relaxation of Debye type and its relaxation frequency is as high as one hundred kHz. The profile of the third-order nonlinear dielectric spectrum varies in complex fashion with temperature. In the vicinity of the SmA-SmC_α* phase transition, experimentally obtained nonlinear spectra are well described by those calculated with phenomenological theory of Landau type. The soft mode of the SmC_α* phase shows critical slowing-down near the transition temperature. In the lower-temperature region of the SmC_α* phase, the contribution from the soft mode of the SmC_α* phase reduces and the other relaxation mode with Debye-type spectrum appears at several hundred Hz in the nonlinear spectrum. The appearance of this low-frequency mode suggests that the cooperative fluctuation of directors over long range exists in the SmC_α* phase. Received 19 April 2002 and Received in final form 23 July 2002 RID="a" ID="a"e-mail: kimura@exp.t.u-tokyo.ac.jp