Thermodynamic and electrical characteristics of the twisted grain boundary phases of 4-n-dodecyloxy-4′-(cholesteryloxycarbonyl-1-butyloxy) chalcone

The investigated optically active dimeric compound, 4-n-dodecyloxy-4′-(cholesteryloxycarbonyl-1-butyloxy) chalcone, shows wide temperature ranges of two twisted grain boundary (TGB) phases, namely TGBA and TGBC*. The dielectric spectroscopy has been carried out for this compound in the frequency range of 1?Hz to 35?MHz for two different conditions of molecular anchoring. A relaxation mode has been detected in the TGBA and TGBC* phases for the planar anchoring of the molecules. This mode lies in the MHz region and has the characteristics of amplitude fluctuation of directors (soft mode). Results are supportive of the theory developed for the soft modes of TGBA and TGBC* phases. Dielectric anisotropy shows an unusual but characteristic (of TGB phases) variation with temperature.     

Twisted-grain-boundary (TGB) phases: nanostructured liquid-crystal analogue of Abrikosov vortex lattices

Twisted-grain-boundary (TGB) phases shown by some liquid-crystalline materials have properties common to those of both smectic and cholesteric phases. Following analogy between liquid crystals and super conductors proposed by de Gennes [Solid State Commun., 10, 753 (1972)], Renn and Lubensky [Phys. Rev. A, 38, 2132 (1988)] theoretically predicted a chiral analog of the smectic A (SmA*) phase, which is now known as TGBA phase. The TGBA phase was experimentally observed for the first time by Goodby et al. [Nature, 337, 449 (1989)] in the chiral homologous series of ferroelectric liquid-crystal material R- and S-1-methylheptyl 4′-[(4′′-n-alkoxyphenyl)propionoyloxy]-biphenyl-4-carboxylates (nP₁M₇), with n?=?13,14,15. Since then, more than a hundred pure and mixed systems showing TGBA phase have been found. Later, Renn derived a mean-field phase diagram based on the chiral Chen-Lubensky model, and predicted two more TGB phases, namely TGBC and TGBC?. These two phases have also been experimentally observed in many systems, and in a few, the phase diagram is similar to that predicted by Renn. Unlike the TGBA phase, several theoretical models have been proposed for TGBC and TGBC? phases, and it remains to be ascertained whether all the types of proposed TGBC/TGBC? structures experimentally exist. A review of the theoretically predicted and experimentally observed TGB phases is given in the present article. Some recently observed novel optical textures of the TGB phases are also reported.     

Frequency and temperature dependence of the dielectric parameters of wide temperature range TGBA and TGBC* phases of unsymmetrical liquid crystal dimers

In the present work we have carried out frequency and temperature dependent dielectric studies of an optically active dimeric compound, 4-n-undecyloxy-4′-(cholesteryloxycarbonyl-1-butyloxy)chalcone which shows wide temperature range twist grain boundary (TGB) phases namely TGBA and TGBC*. Dielectric permittivities and DC conductivities have been determined along and normal to the TGB helix axes. Two weak collective modes of dielectric relaxations have been detected for the planar oriented sample where permittivity is measured normal to the long axes of the molecules (but along the TGB helix axis). One mode, which exists in the MHz region, has behavior similar to those of the soft mode due to the amplitude fluctuation. The second one exists in the low frequency region (～100 Hz) and appears due to phase fluctuation as happens in the case of Goldstone mode. Sample confined between electrodes treated for the homeotropic alignment (permittivity measured normal to the helix axis) does not show any mode of relaxation in the frequency range of 1 Hz to 1 MHz. Measured permittivities suggest negative dielectric anisotropy for the system.     

Twisted Grain Boundary Phases in the Binary Mixtures of 3ß-Chloro-5-Cholestene and 4-N-Decyloxybenzoic Acid

From the thermodynamical, optical texture and dielectric studies of the binary mixtures of 3β-chloro-5-cholestene (ChCl) and 4-n-decyloxybenzoic acid (DOBA), the phase diagram has been drawn. It has been observed that low concentrations of ChCl (1 to 7 mol%) in DOBA induce various types of twisted grain boundary (TGB) submesophases, whereas higher concentrations induce a smectic A (SmA) mesophase. Various optical textures of the TGB phases under different conditions of molecular anchoring have been observed. Weak transitions related with TGB phases have been detected from the temperature dependence of dielectric permittivity. The observed phase diagram of ChCl-DOBA binary system is in complete conformity with the theoretically predicted mean-field phase diagram derived by Renn within the framework of the chiral Chen-Lubenski model     

Induced twisted-grain-boundary phases in the binary mixtures of a cholesteric and a nematic compound

Thermodynamical, optical-texture and dielectric studies have been performed to study the phase diagram of the binary system of 5-cholesten-3β-ol-octanoate and 4-n-nonyloxybenzoic acid. It is observed that low concentrations of 5-cholesten-3β-ol-octanoate (2–30?mol?%) in 4-n-nonyloxybenzoic acid induce a mean-field phase diagram derived by Renn within the framework of the chiral Chen–Lubenski model. Various optical textures of the twisted-grain-boundary (TGB) phases under different conditions of molecular anchoring have been observed. Weak transitions related to the TGB phases have been detected by temperature dependent dielectric spectroscopy.     

Novel twist grain boundary smectic-C phases

Several new kinds of smectic-C twist grain boundary phases (TGBC) have been observed during the last few years. These pure compounds or mixtures exhibit unusual textures with polygonal lattices (square or hexagonal grids) in the plane normal to the TGB helix. The structure of these new phases seems to be complex and different from reported and predicted TGBC phases. In this article, we review the main results obtained on these different new phases, and we propose new TGBC structures based on the well-known splayed polarization --twisted director structures adopted by chiral smectic-C's in planar aligned (bookshelf) cells. The observed square or hexagonal lattices are made of superimposed pairs of unwinding lines due to the suppression of the helix within smectic-C blocks by the grain boundaries (unwinding walls). A lattice-free TGBC occurs if the helix within smectic-C blocks is suppressed completely. Received 15 March 2001     

Frustrated smectic liquid crystalline phases in lactic acid derivatives

ABSTRACT

We have prepared and studied a series of compounds with different types of molecular core and lactate unit in the chiral terminal chain. We draw a survey and comparison of their mesomorphic properties with respect to the occurrence of twist grain boundary (TGB) phases. The materials exhibit extremely wide TGBA phase more than 60K broad, unique TGBA-TGBC-SmC*-SmC_A* phase sequence and unique re-entrant TGBA phase below the SmA phase. TGB phases have been induced in binary mixtures of molecules with different molecular shape and chirality (chiral lactic acid derivative and non-chiral hockey-stick mesogen). Unique effect is observed for compounds with TGBA phase, where the applied electric field transforms the planar texture into the homeotropic one, homogeneously dark in crossed polarizers. The process is analogy of the Frederiks transition so far known only for nematics. This effect, changing the bright state to the dark one, is promising for applications.     

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.     

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.     

Study on optical characterization of TGB and reentrant smectic-A phases in binary mixture of two liquid crystals

In this work, our investigation is to study the optical and thermal properties of the binary mixture of cholesteric and nematic compounds, namely, cholesteryl nonanoate and p-methoxybenzylidene-p-ethylaniline, which exhibits a very interesting liquid crystalline twisted grain boundary (TGB) phase and reentrant smectic-A phase. The chiral liquid crystalline TGB phases and reentrant smectic-A phases have been observed at different concentrations and at different temperatures. The existence of TGB and reentrant smectic-A phases is confirmed by differential scanning calorimetry and optical microscopic studies. The variation of optical anisotropy has been discussed. The helical pitch of the cholesteric phase has also been discussed.     

Dielectric spectroscopy of a high-polarization ferroelectric liquid crystal

Dielectric spectroscopy investigations in the frequency range 50?Hz to 1?MHz have been carried out on a new ferroelectric liquid-crystalline material (S-(-)-4-(2-n-hexylpropionyloxy)biphenyl-4′-(3-methyl-4-decyloxy)benzoate) possessing a relatively large spontaneous polarization (P _s?～?240?nC?cm^?2) and containing a lateral methyl group on the aromatic ring of the alkoxybenzoate unit. The effect of temperature on the dielectric relaxation modes has been investigated in the SmC* and N* phases. From dielectric dispersion data, relaxation frequency and dielectric strength of all detected relaxation modes have been evaluated and discussed. A new surface-like mode of relaxation frequency ～11?kHz and dielectric strength 3.8, is seen to appear in the SmC* phase.     

Pattern formation at the traveling liquid-crystal twist grain boundary-smectic a interface

Summary Pattern formation at phase boundaries moving in a temperature gradient is one of the major areas of nonequilibrium physics attracting considerable attention. While most of the early work concentrated on the moving solid-liquid interface, now the focus has changed to phase transitions characterized by broken continuous symmetry. Most recently we investigated consequences to interfacial patterns of a chirality-induced equilibrium length. Here we study patterns at another chiral interface where one of the phases has a chirality-induced defect lattice, the twist grain boundary (TGB) phase. The TGB state is analogous to the vortex lattice in Type-II superconductors predicted by the Gennes’ analogy between the nematic (N)-smectic A (A) transition and the normal-superconducting transition. In this analogy, a cholesteric A transition is analogous to the normal-superconducting transition in an external magnetic field and a theory has been developed for its analogous vortex lattice, the TGB phase, when this transition is Type II. We study patterns formed at the traveling TGB-A phase boundary. Different patterns are observed depending on whether TGB grows into A or A into TGB. Indeed, this maybe the first time a steady-state pattern is observed in directional melting (i.e. TGB growing into A). As these patterns have a broad band of wavelengths, they are difficult to characterize physically. Thus, we introduced a novel analysis (most simply but not rigorously described as) measuring the fractal dimension of the patterns at these traveling interfaces. Two lengths emerged from this analysis: a longer one set by sample thickness and a shorter one set by the smallest TGB unit that can grow into an oriented smectic A phase. We invoke our old dynamic arguments to account for why TGB cannot propagate at a second-order TGB-cholesteric phase transition so it is eventually squeezed out leaving behind a direct cholesteric-A transition. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

The commensurate and incommensurate TGBC^* liquid crystal phases

We propose complements to the Renn model of the liquid crystal TGBC^* phase. We argue that the rotation angle per helislab is spontaneously in the radian range, not too small to limit the energy cost of the twist grain boundaries between the helislabs, not too large to preserve the double twisting efficiency. Taking the elastic interactions between the helislabs into account, we show that the structure may undergo two different lock-ins, provided that the uncontrolled interactions at the sample surfaces are small enough. First, for appropriate values of the elastic constants, an angular lock-in may fix the rotation angle per helislab at values exactly commensurate to π. Three characteristic lengths of the TGBC^* phase, the TGB period and the thicknesses of both the smectic blocks and of the helislabs are then commensurate to one another, with moreover, integer ratios at the most efficient commensurabilities. The TGBC^* phase could thus exist in several versions, incommensurate and commensurate, according to the steps of a restricted Devil's staircase. A second elastic lock-in should then arise in the commensurate TGBC^* phases, to set the arrays of disclination lines between the helislabs in simple rectangular lattices, arranged in a helical manner. Being placed right behind one another, the disclination lines then coincide when observed along the TGB axis. This could explain the typical textures with square or hexagonal grids, observed in oriented samples. The commensurability of the TGBC^* phases could be analyzed with X-ray scattering experiments in the same manner as already reported for the TGBC phase. Received 30 November 1999 and Received in final form 5 May 2000     

Observation of a reentrant twist grain boundary phase

We report the occurrence of a reentrant twist grain boundary phase, which we designate as Re- TGB(A). Microscopic observations on a nonsymmetric dimer showed the phase sequence Iso- N*- TGB(A)-Sm- A-Re- TGB(A)- TGB(C*). Here N* and Sm- A stand for the chiral nematic and smectic- A phases, TGB(A) is the twist grain boundary phase with smectic- A blocks, and TGB(C*) that with smectic- C* blocks and exhibiting features of both the smectic- C* and TGB phases. The reentrance of the TGB(A) phase is unambiguously demonstrated using x-ray diffraction, selective reflection, and optical rotation data.     

Experimental investigations of a new TGBC mesophase

We report on optical and structural X-ray studies on a smectic C twist grain boundary phase (TGB) of a pure liquid crystalline material. It is shown that this TGB phase, which exists over a large range of temperature, is definitely different from previously reported and predicted TGB phases. The two main experimental features are: (i) the observation in planar geometry of an optical texture exhibiting a square grid pattern, and (ii) the detection of a broad Bragg ring in reciprocal space instead of one (TGB) or two (TGB) sharp rings. We suggest a few possible tracks that can be explored to understand the complex structure of this new phase. Received 25 January 1999     

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.     

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     

Observation of dielectric relaxation modes in chiral smectic C liquid crystal mixture

The dielectric parameters in the frequency range 50 Hz to 1 MHz have been measured in a SmC* liquid crystal mixture in planar alignment. The relaxation frequency (f_r), distribution parameter (α) and dielectric strength (δε) have been evaluated and their corresponding values were found to be 206.62 Hz, 0.06 and 114.6 respectively. The Goldstone mode, domain mode, soft mode and a new relaxation mode have been observed.