Piezoelectric effect in liquid crystals

A piezoelectric effect has been observed in a cholesteric liquid crystal layer (an electric field effect type, a mixture of cholesteryl oleyl carbonate, cholesteryl chloride and cholesteryl nonanoate) [1]. The layer, subjected to shear vibration, generates an alternating electric potential of the same frequency as the exciting vibration. In the present paper an extension of these investigations is reported to cases with various mixing ratios and also to one of smectic liquid crystals (lecithin with water). For a cholesteric liquid crystal of a particular mixing ratio, the strength of the electric generation is found to reach as high as 450 mV(p-p) for a vibratory shear displacement of 1 μm(p-p) under a certain molecular orientation preparation. Small electric generation is also observed for the above smectic liquid crystal but not for the nematic liquid crystals (MBBA and EBBA). A simple continuum elasticity model can qualitatively explain the behaviour of this electric potential generation.     

Solid-state morphology of aromatic-aliphatic polyester crystallized from smectic liquid crystal

The solid-state morphology of poly(hexamethylene p,p'-bi-benzoate) (BB-6) and its dependence on the texture of the smectic liquid crystal state from which it crystallized were studied using electron microscopy, polarizing optical microscopy, and small-angle x-ray diffractometry. Thin films of BB-6 suitable for the microscopy were prepared by casting a hot solution of the polymer in tetrabromoethane onto mica at 150°C. The as-cast film of BB-6 was first heated to 260°C, maintained in the smectic range (210°C), and then cooled gradually to room temperature. A number of types of defect structures—such as Dupan cyclides, edge dislocation, tilt walls, and disclinations — were observed in the solid BB-6 formed from the smectic melt. On the basis of the electron microscopy and small-angle x-ray diffractometry, it is suggested that folded-chain crystals are formed during the crystallization from the smectic melt. Electron microscopic observations of the solid BB-6 and its orientation behavior under shear can be reasonably explained by assuming the presence of a precursory chain-folded layer structure in the smectic liquid crystal of BB-6.     

Electric-field-induced chirality flipping in smectic liquid crystals: the role of anisotropic viscosity

We demonstrate the homogeneous and permanent reversal of the chirality of a condensed phase by an applied electric field. Tilted chiral smectic layers exhibit a coupled polarization density and molecular orientation fields which reorient about the layer normal as couple of fixed handedness in response to small applied electric fields. Experiments on some bent-core smectics show that above a threshold field the induced rotation can occur instead about the molecular long axis and that, as a result, the handedness of the phase can be flipped. The effect is quantitatively described by a nonequilibrium dissipative model of chiral smectic dynamics with anisotropic rotational viscosities.     

Effect of electric field on the rheology of ferroelectric liquid crystal MORA-8

Effects of electric field on the rheology, electrorheological effects, are investigated on ferroelectric smectic C* phase of 4-(6-methyl)octyl-resorcylidene-4′-octylaniline (MORA-8). When an electric field is applied in smectic C* phase, an increase of the shear stress is observed with its behavior depending on the shear rates; at higher shear rates the shear stress increases monotonously with the electric field strength, but at lower shear rates the shear stress increases monotonously until about 2 kV mm⁻¹, but above this field it discontinuously decreases to lower values, which is followed by an increase at higher electric fields. In close vicinity of the smectic C* to isotropic phase transition point, a field induced decrease of the shear stress is observed. These ER behaviors are discussed on the basis of the field induced orientational changes of the smectic layer and the director and a possible field induced structural change.     

Order and strain in main-chain smectic liquid-crystalline polymers and elastomers

The layer correlations in main-chain smectic liquid-crystal polymer and elastomer systems have been studied using high-resolution X-ray scattering. In contrast to side-chain smectic polymers, in main-chain systems the polymer chains are oriented parallel to the layer normal. As a result they couple directly to the lamellar structure and any polymer defect is translated into layer distortions. For the homopolymers the resulting X-ray lineshapes are well described by Lorentzians. This is interpreted as an average of algebraically decaying order in domains with dimensions of hundreds of nm and a wide dispersion of sizes. The elastomers show much broader peaks than the correponding polymers. This is attributed to strong non-uniform strain within the finite-size domains due to defects of the layer structure. An erratum to this article is available at .     

Molecular models for ferroelectric liquid crystals with conventional and anomalously weak layer contraction

A molecular theory of the ferroelectric smectic C* phase has been developed using the simple model of a chiral molecule composed of a uniaxial core and a pair of off-center nonparallel dipoles which determine molecular chirality and polarity. The interaction between uniaxial cores is modeled by a rather general effective potential which can be used to describe smectic materials with both conventional and anomalously weak layer contraction in the smectic C* phase. Spontaneous polarization, tilt, and layer spacing are calculated numerically as functions of temperature, and it is shown that the variation of the polarization generally deviates from that of the tilt angle. It is shown that this deviation is more pronounced in smectic materials tilting with low layer contraction which corresponds to existing experimental data. The model has been used to reproduce qualitatively the experimental data for polarization, tilt and layer spacing for two similar mixtures exhibiting conventional and anomalously weak layer contraction. The polarization and the tilt are also calculated in the case when the smectic A-smectic C* transition is characterized by the biaxial primary order parameter.     

Electroclinic effect in free-standing smectic elastomer films

The coupling of the mesogenic tilt in smectic liquid crystals to external electric fields in the layer plane (electroclinic effect) provides an opportunity to control the smectic layer thickness with electric fields. In ordered ferroelectric smectic elastomers it is possible to achieve a macroscopic electromechanical response. The effect is particularly pronounced near the smectic A-to-smectic C^* phase-transition temperature. In this work, the electrostriction of weakly cross-linked smectic elastomers is studied by means of optical interferometry of thin films. Its observed magnitude corresponds to an induced tilt of approximately 7.7°, yielding a layer contraction of 1%, in a 3 MV/m electric field. This value is in agreement with earlier measurements of tilt susceptibility in a structurally similar polymer, but is considerably smaller than previously reported data on elastomers with a comparable chemical structure. PACS 61.30.Vx; 83.80.Va; 77.65.Bn     

Partitioning of a heterotelechelic polystyrene to separate interfaces of thin films

Heterotelechelic deuteropolystyrenes have been synthesised with a tertiary amine functionality at one end and a fluorocarbon group at the other end of the polymer chain. A layer of this polymer, circa 120 ? thick, has been attached to the surface of a silicon substrate and subsequently covered with a much thicker layer of hydrogenous polystyrene. The combination has then been annealed at 413 K under vacuum for defined times and the subsequent distribution of the deutero heterotelechelic polymer determined using nuclear reaction analysis and neutron reflectometry. The influences of annealing time, molecular weight and thickness of the hydrogenous polymer have been examined. Nuclear reaction analysis showed that an excess of the heterotelechelic polymer formed at both interfaces with a larger excess remaining at the substrate-polymer interface. When the molecular weight of the hydrogenous polymer is lower than that of the deuteropolymer, the deutero layer is initially swollen by the hydrogenous polymer but the thickness then decreases as deutero polymer becomes detached from the silicon substrate and an additional excess layer is eventually formed at the vacuum-polymer surface. When the molecular weight of the hydrogenous polymer is higher, there is an initial shrinkage of the deuteropolymer layer, but the original thickness (∼ radius of gyration of the deuteropolymer) is regained on prolonged annealing. There is no evidence for bridging between the two interfaces by the heterotelechelic polymer. After five days annealing the volume fraction distribution of the deuteropolymer at the silicon substrate was well described by a self-consistent field model where the only adjustable parameter was the sticking energy of the tertiary amine group to the silicon substrate for which a value of 8k _B T was obtained. Comparison of the dependence of the equilibrium layer thickness of the deuteropolymer on the equilibrium grafting density at the silicon surface with the predictions of scaling theory for brush-like polymer layers suggested that the grafted molecules were in the ideal, unperturbed brush region. Received 12 October 2000 and Received in final form 27 March 2001     

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.     

Statistics of tumbling of a single polymer molecule in shear flow

We present experimental results on statistics of polymer orientation angles relative to the shear plane and tumbling times in shear flow with thermal noise. The strong deviation of the probability distribution functions (PDFs) of the orientation angles from Gaussian PDFs was observed in good accord with theory. A universal exponential PDF tail for the tumbling times and its predicted scaling with Wi (that is, the dimensionless shear rate normalized by the polymer relaxation time) are also tested experimentally against numerics. The scaling relations of PDF widths for both angles as a function of Wi are verified and compared with numerics.     

Statistical Physics Approach to Liquid Crystals: Dynamics of Mobile Potts Model Leading to Smectic Phase,Phase Transition by Wang–Landau Method

We study the nature of the smectic–isotropic phase transition using a mobile 6-state Potts model. Each Potts state represents a molecular orientation. We show that with the choice of an appropriate microscopic Hamiltonian describing the interaction between individual molecules modeled by a mobile 6-state Potts spins, we observe the smectic phase dynamically formed when we cool the molecules from the isotropic phase to low temperatures (T). In order to elucidate the order of the transition and the low-T properties, we use the high-performance Wang–Landau flat energy-histogram technique. We show that the smectic phase goes to the liquid (isotropic) phase by melting/evaporating layer by layer starting from the film surface with increasing T. At a higher T, the whole remaining layers become orientationally disordered. The melting of each layer is characterized by a peak of the specific heat. Such a succession of partial transitions cannot be seen by the Metropolis algorithm. The successive layer meltings/evaporations at low T are found to have a first-order character by examining the energy histogram. These results are in agreement with experiments performed on some smectic liquid crystals.     

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.     

EPR Investigations on Molecular Orientation of Paramagnetic Liquid Crystals in a Surface-Stabilized Liquid Crystal Cell: Studies on a Smectic C or Chiral Smectic C Phase

By electron paramagnetic resonance spectroscopy we investigated the molecular orientation in a surface-stabilized liquid crystal (LC) cell, which includes a racemic (±) or an enantiomerically enriched (S,S) paramagnetic LC, (2S,5S)-2,5-dimethyl-2-tridecyloxyphenyl-5-[4-(4-tridecyloxy-benzenecarbonyloxy)phenyl]pyrrolidine-1-oxy (2), whose spin source is fixed inside the rigid core. For both the smectic C (SmC) phase of (±)-2 and the chiral smectic C (SmC^*) phase of (S,S)-2 in a surface-stabilized LC cell (antiparallel configuration, thickness of 4 μm), the profile of the observed g-value as a function of the angle between the applied magnetic field and the cell plane could be explained by the orientation model, where, with some disordering, the molecules align uniformly with the direction which tilts from the normal line of the smectic layer being orthogonal to the rubbing direction on the cell surface. We divided the effect from the disordering into two parts, one of which is concerning the direction of the molecular long axis and the other is concerning the rotation around the molecular long axis. As a result of the analysis, the SmC^* phase gave quite lower ordering concerning the direction of the molecular long axis and a little lower ordering concerning the rotation around the molecular long axis than the SmC phase at the same temperature (80 °C). The obtained lower ordering in the SmC^* phase is probably due to the chirality that would result in the formation of a helical superstructure in a bulky state. Authors' address: Yohei Noda, Laboratory of Electron Spin Chemistry, Department of Chemistry, Graduate School of Science, Kyoto University, 606-8502 Kyoto, Japan     

Effect of fluorination of molecular rigid core in liquid crystal biphenyl benzoate based homologous series

Liquid crystalline perfluorinated biphenyl benzoates were synthesized and investigated. A highly tilted, neat orthoconic smectic antiferroelectric phase was observed. A homologous series of compounds without and with a single fluorine atom substituted at different positions of a molecular rigid core was investigated by standard methods. Influence of fluorine substitution on physical properties of antiferroelectric smectic phase was discussed as well as influence of fluorination on molecular dipole moment orientation and its value were presented. Decrease in rotational viscosity as a result of fluorine substitution within a molecular rigid core was ascribed to changes of molecular packing.     

Shear instabilities of freely standing thermotropic smectic- A films

In this Letter we discuss theoretically the instabilities of thermotropic freely standing smectic- A films under shear flow [3]. We show that, in Couette geometry, the centrifugal force pushes the liquid crystal toward the outer boundary and induces smectic layer dilation close to the outer boundary. Under strong shear, this effect induces a layer buckling instability. The critical shear rate is proportional to 1/sqrt[d], where d is the thickness of the film.     

Angular dependent linewidths for a spin probe dissolved in a liquid crystal

A spin probe dissolved in the mesophase of a nematic or smectic liquid crystal behaves, in many ways, as if it were encorporated in a uniaxial single crystal. For example the positions of the lines in the electron resonance spectrum of the probe depend on the orientation of the liquid crystal with respect to the magnetic field. In addition the widths of the spectral lines might also be expected to be angular dependent. The form of this angular dependence is readily calculated provided the dominant spin relaxation process results from molecular reorientation with respect to the director in the mesophase. In this paper we develop a theory for the angular dependence of the linewidths and show how it could be used, with some advantage, to investigate molecular reorientation in a macroscopically anisotropic system. The observed angular dependence of the linewidths for a nitroxide spin probe dissolved in the mesophase of a smectic A liquid crystal confirms certain aspects of the theory.     

Transformation of the structure of smectic liquid crystals associated with frustration and the surface of ultrathin films

Frustrations associated with competition between interlayer interactions in smectic liquid crystals and geometric frustrations are responsible for variety of interesting physical phenomena, formation of unusual structures, and transitions between them. Owing to the possibility of the preparation of ultrathin freely suspended smectic nanofilms and a single-layer change in their thickness (by one molecular layer), smectic films are unique objects for the study of ordered structures in a limited geometry. Effects associated with frustration and the nanothickness of smectic films have been discussed.     

Correlation between the molecular chirality index and the spontaneous polarisation in series of smectic C* liquid crystals

A correlation between spontaneous polarisation and the chirality index of the constituent molecules, multiplied by the molecular transverse dipole, has been considered for five series of ferroelectric smectic C* liquid crystals. A good correlation has been found within each series, and it has been shown that the scaled chirality index may be used to estimate the spontaneous polarisation in a series of smectic C* mesogens with small systematic changes of the molecular structure. At the same time one cannot expect any significant correlation between the polarisation and the chirality index for smectic C* materials of sufficiently different structure because the spontaneous polarisation may be significantly effected by some details of the molecule's structure including the orientation of the transverse dipole with respect to the primary short molecular axis.     

Main-chain smectic liquid-crystalline polymers as randomly disordered systems

We report a high-resolution X-ray lineshape study of main-chain smectic polymers. The results indicate that the layer ordering differs fundamentally from the algebraic decay typical for other smectic liquid-crystalline systems. The lineshapes are best described by broad squared Lorentzians indicating some form of short-range correlations. However, several higher harmonics are observed, which excludes simple liquid-like short-range order. This behaviour is tentatively attributed to a random field of defects associated with entangled hairpins in the main-chain polymer structure.