Molecular structure and physical parameters of some ferroelectric liquid crystal systems

We investigate thermodynamic properties and spontaneous polarization of ferroelectric liquid crystal (SmC^*LC) systems: smectic C matrix + chiral adding (ChA). The fact of existence of an optimum concentration of ChA, for which the studied SmC^*LC systems have the maximum value of spontaneous polarization, and a certain concentration, at which the phase transition of the chiral tilted smectic C phase to the smectic A phase occurs, is established. Temperature dependence curves for the free energy, configuration energy, specific heat, and the orientational order parameter are calculated in the temperature range of existence of liquid crystal mesophases. The curves are in good agreement with the experimentally observed trends of the SmC^*LC properties.     

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.     

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.     

Investigation of new chiral fluorosubstituted compound exhibiting room temperature antiferroelectric phase

Influence of the electric field upon alignment of molecules in ferro- and antiferroelectric phases has been studied for two fluoro-substituted compounds exhibiting antiferroelectric phase at room temperature. Two different relaxation processes have been revealed in the ferroelectric as well as antiferroelectric phase. Low temperature value of spontaneous polarization is ca. 130 nC/cm² for both substances studied. The substances align very well in the external electric field — a mono-domain of the ferroelectric SmC* phase can be obtained in about 3.5 hours.     

A study of polarization in smectic liquid crystals via statistical-physics methods

The spontaneous polarization processes in synclinic and anticlinic smectic liquid crystals are discussed in the context of molecular statistical theory. The effects of interaction between molecules, external electric fields, and bending of molecules via polarization are elucidated as well.     

Symmetries and induced effects in bilayer and multilayer antiferroelectric and ferrielectric liquid crystal phases

The stable antiferroelectric and ferrielectric smectic phases which may arise below a chiral SmA* phase are investigated theoretically. The symmetry and physical properties of the bilayer and multilayer configurations are worked out. Antiferroelectric and ferrielectric bilayer and multilayer configurations, possessing an induced spontaneous ferroelectric polarization component perpendicular to the smectic layers, are shown to take place, as the result of a nonlinear piezoelectric effect. These states of low polar symmetries occur when the angle between the inlayer projections of the dipoles and the director of the molecules is different from 90 degrees.     

Ultrasound-promoted synthesis of 3-trichloromethyl-5-alkyl(aryl)-1,2,4-oxadiazoles

The alternative synthesis of 12 1,2,4-oxadiazoles using ultrasound irradiation from trichloroacetoamidoxime and acyl chlorides is reported. Seven of them are novel compounds. The 3-trichloromethyl-5alkyl(aryl)-1,2,4-oxadiazoles have been synthesised in better yields and shorter reaction times compared to the conventional method. This protocol can be applicable for preparation of 1,2,4-oxadiazoles containing aryl or alkyl groups attached at their C-5 side-chain.     

Bilayer-by-bilayer antiferroelectric ordering in freely suspended films of an achiral polymer-monomer liquid crystal mixture

Thin freely suspended films of a mixture of an achiral side-chain liquid crystal polymer and its monomer have been studied with depolarized reflected light microscopy. We observe that regions with an odd number of bilayers exhibit a net spontaneous polarization in the tilt plane of the molecules, while regions with an even number of bilayers have no net polarization. These odd-even effects are direct evidence that the tilted smectic bilayers are anticlinic at the polymer backbone and synclinic at bilayer interface and confirm that the phase is bilayer-by-bilayer antiferroelectric.     

A molecular theory of smectic C liquid crystals made of rod-like molecules

Organic compounds exhibiting the smectic C phase are made of rod-like molecules that have dipolar groups with lateral components. We argue that the off-axis character of the lateral dipolar groups can account for tilt in layered smectics (SmC, SmC*, SmI etc.). We develop a mean-field theory of the smectic C phase based on a single-particle potential of the form U _C ∝ sin(2θ)cosφ, consistent with the biaxial nature of the phase, where θ and φ are the polar and azimuthal angles, respectively. The hard-rod interactions that favour the smectic A phase with zero tilt angle are also included. The theoretical phase diagrams compare favourably with experimental trends. Our theory also leads to the following results: i) a first-order smectic C to smectic A transition above some value of the McMillan parameter α, leading to a tricritical point on the smectic C to smectic A transition line and ii) a first-order smectic C to smectic C transition over a very small range of values of the model parameters. We have also extended the theory to include the next higher-order term in the tilting potential and to include the effect of different tilt angles for the molecular core and the chain in the SmC phase. Received 3 August 2002 RID="a" ID="a"Present address: Department of Physics, Vijaya College, R. V. Road, Bangalore - 560 004, India. RID="b" ID="b"e-mail: nvmadhu@rri.res.in     

On some liquid crystalline phases exhibited by compounds made of bent-core molecules and their mixtures with rod-like molecules

In most homologous series of compounds made of bent-core (BC) molecules, the B₂ B₁ and B₆ phases occur as the chain length decreases. We have studied binary mixtures of the compound 1,3-phenylene bis[4-(3-methylbenzoyloxy)]4-n-dodecylbiphenyl 4’-carboxylate (BC12) which exhibits the B₂ phase with the compound 4-biphenylyl 4’-n-undecyloxybenzoate (BO11) made of rod-like (R) molecules. We find the above sequence of occurrence of the B phases with increasing concentration of BOH. In this paper we describe the physical origin for the formation of these phases in both pure compounds and in the mixtures. We have also found the occurrence of the biaxial smectic A phase when the BO11 concentration is increased to 87–95.5 mol%. We also report on another binary system composed of BC12 and 4-n-octyloxy 4’- cyanobiphenyl (8OCB) made of R molecules. This system exhibits the biaxial smectic A phase down to 30°C. Using polarized infrared spectroscopy we find that the mutual orientation of the R and BC molecules in the SmA_db liquid crystal is such that the arrow axes of the BC molecules are along the layer normal of the partial bilayer smectic structure formed by the rods. We also describe unusual growth patterns obtained when the nematic phase transforms to the SmA_db phase in a mixture with 24 mol% of BC12.     

Biaxial modeling of the structure of the chevron interface in smectic liquid crystals

We have included the inherent molecular biaxiality of the smectic C phase in a model of the chevron structure. This molecular biaxiality is related to a hindered rotation about the molecular long axis which for chiral, polar molecules induces a spontaneous polarization. Through the coupling between biaxiality and the smectic cone angle, continuity of the molecular distribution at the chevron interface leads to changes in the cone angle. Under certain approximations we are able to find analytic expressions for the chevron structure and consequently estimate the width of the chevron interface. There are in fact two correlation lengths which govern variations in the cone angle and the biaxiality.     

SWCNT doped ferroelectric liquid crystal: The electro-optical properties with enhanced dipolar contribution

Effect of single wall carbon nanotubes (SWCNTs) on electro-optical performance of a ferroelectric liquid crystal (FLC) has been studied. Voltage dependent spontaneous polarization and response time measurement has been made for the pure and SWCNT doped FLC system. Dielectric measurement has also been performed to understand the existing interaction between SWCNTs and FLC molecules. The results have shown increase in the value of spontaneous polarization and relative permittivity with slight slower response for the doped system. The observed properties of doped system revealed that the SWCNTs can perform well with FLC at low applied electric field to enhance the performance of LC devices.     

Phase transitions in nanocomposites of hydrogen-bonded dimeric liquid crystals with mesogenic and non-mesogenic components

Microtextural polarization, phase transitions, and electro-optical effects are studied in a series of nanocomposites, grown by mixing alkyloxybenzoic acids (nOBAs), displaying hydrogen-bonded dimeric liquid crystal (LC) state, with non-mesogens (single-walled carbon nanotubes (SWCNTs), perfluorooctanoic acid) or mesogens (bent-core LC compound D14F3). Each of the studied nanocomposites, in which the nOBA serves as a matrix, forms complexes with bent-shaped dimeric, caused by the interaction between the dopant structural units and the dimer rings. This feature, coordinated with the surface anchoring, bulk and electrical effects, leads to drastic reduction of the LC system symmetry. As a result, transitions from achiral (characteristic for the pristine nOBA) to chiral states (including ferroelectric smectic C with C₂ symmetry and ferroelectric smectic C_G with the lowest C₁ triclinic one) take place. The functionalization of the SWCNTs causes drastic increase of the ferroelectricity.     

Structural,dielectric, electrical and piezoelectric properties of Ba<Subscript>4</Subscript>SrRTi<Subscript>3</Subscript>V<Subscript>7</Subscript>O<Subscript>30</Subscript> (R=Sm,Dy) ceramics

Polycrystalline samples of Ba₄SrRTi₃V₇O₃₀ (R=Sm and Dy), members of the tungsten-bronze family, were prepared using a high-temperature, solid-state reaction technique and studied their electrical properties (using complex impedance spectroscopy) in a wide range of temperature (31–500°C) and frequency (1 kHz-1 MHz). Preliminary structural (XRD) analyses of these compounds show the formation of single-phase, orthorhombic structures at room temperature. The scanning electron micrographs (SEM) provided information on the quality of the samples and uniform distribution of grains over the entire surface of the samples. Detailed studies of the dielectric properties suggest that they have undergone ferroelectric-paraelectric phase transition well above the room temperatures (i.e., 432 and 355°C for R= Sm and Dy, respectively, at frequency 100 kHz). Measurements of electrical conductivity (ac and dc) as a function of temperature suggest that the compounds have semiconducting properties much above the room temperature, with negative temperature coefficient of resistance (NTCR) behavior. The existence of ferroelectricity in these compounds was confirmed from a polarization study.      

Ferroelectric phase transition in Langmuir-Blodgett films of copper phthalocyanine

A ferroelectric phase transition is observed in Langmuir-Blodgett films prepared from substituted copper phthalocyanine molecules. The linear and nonlinear dielectric properties of the films and the switching of their spontaneous polarization are investigated in the temperature range of the phase transition. The observed features can be explained by the Landau-Ginzburg model of a first-order phase transition. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 9, 625–631 (10 November 1999)     

Dynamics of domain-wall motion in ferroelectric liquid crystals in an electric field

The director reorientation in smectic liquid crystals with ferroelectric properties has been considered in the case where the interaction of liquid-crystal molecules with the surface leads to a partial unwinding of the helical structure of the liquid crystal and the reorientation occurs as a result of the domain-wall motion. The dependences of the velocity of domain-wall motion on the electric field strength, electric field variation frequency, boundary conditions, spontaneous polarization, and viscosity of the liquid crystal have been determined. It has been demonstrated that an increase in the electric field variation frequency or the polar part of the anchoring energy and the spontaneous polarization of the liquid crystal at a constant field frequency results in an increase of the velocity of domain-wall motion. As a consequence, the time of the electro-optic response of the liquid crystal in weak electric fields (from 0.4 to 2.0 V/μm) decreases by a factor of more than three.     

Evidence for triclinic symmetry in smectic liquid crystals of bent-shape molecules.

The first experimental evidence for triclinic symmetry of bulk smectic liquid-crystal samples of achiral banana-shaped molecules is presented. This phase corresponds to the so-called Sm-CG phase consisting of biaxial molecules and characterized by two tilt directions with respect to the layer normal: tilt of the molecular plane (clinic) and tilt of the molecular kink direction (leaning). Each smectic layer has a polarization component normal to the smectic layers (C1 symmetry). The observations suggest that the phase tentatively labeled as B7 is identical with the Sm-CG phase.     

Nonlinear repolarization processes in ferroelectric liquid-crystal thin films

The dynamics of spontaneous polarization switching of the ferroelectric smectic C* in a variable electric field are examined theoretically and experimentally with the help of polarized light scattering. The observed effect of quasiresonant scattering both in freely suspended smectic films and in ordinary electro-optical cells is interpreted within the framework of the nonlinear model of isolated movable kinks in the director orientation distribution. It is shown that the maximum of the scattering intensity at the characteristic frequency of the applied electric field disappears at low temperatures and for small thicknesses of the smectic film. The dependence of the “resonant” frequency on the electric field amplitude, the proximity to the phase transition temperature, the film thickness and thickness of the ferroelectric domains, and also various material parameters is found. Estimates are made of such important characteristics as the dielectric anisotropy, viscosity, and elasticity of the smectic films. The effect of film thickness on the density distribution of the polar anisotropy energy in the film and on the corresponding shape of the moving orientation front within the film are discussed. Zh. éksp. Teor. Fiz. 111, 919–937 (March 1997)     

Dielectric and electrooptical properties of hockey-stick-shaped liquid crystal with a negative dielectric anisotropy

We investigated dielectric properties of a hockey-stick-shaped liquid crystal (HLC). Two dielectric relaxation modes were observed at 0.91 kHz and 4.51 MHz. The low frequency relaxation modes in isotropic, smectic, and nematic phases are related to the motion of ions, collective tilt fluctuation, and rotation around the long molecular axis, respectively. Meanwhile, the high frequency relaxation modes in nematic and smectic phases was due to the rotation around the short axis of the molecules and hindered by the resistance of the ITO layers. We also examined the electrooptical response of the 5.0 wt% HLC-doped commercial nematic liquid crystal (LC) mixtures. The birefringence of the LC mixture was slightly increased, while the falling time and the rotational viscosity was decreased in the nematic phase.