Tilt and temperature dependence of the pitch in the chiral smectic C phase

Abstract

The chirality of the constituent molecules in the chiral smectic phase induces a helical structure with a pitch, p ₀. Because of the tilt and chirality there is a spontaneous polarization and a bend deformation which act upon the induced helix. The resulting pitch is described as a function of p ₀ using the phenomenological theory of a chiral smectic C phase. The pitch, p ₀, is then calculated using a molecular theory of the cholesteric phase. The results obtained explain the experimental observations, at least qualitatively.     

Tilt and temperature dependence of the pitch in the chiral smectic C phase

The chirality of the constituent molecules in the chiral smectic phase induces a helical structure with a pitch, p₀. Because of the tilt and chirality there is a spontaneous polarization and a bend deformation which act upon the induced helix. The resulting pitch is described as a function of p₀ using the phenomenological theory of a chiral smectic C phase. The pitch, p₀, is then calculated using a molecular theory of the cholesteric phase. The results obtained explain the experimental observations, at least qualitatively.     

Phase modulation and ellipticity of the light transmitted through a smectic C* layer with short helix pitch

A chiral ferroelectric smectic C* liquid crystal (FLC) with the helix pitch p ₀?=?330 nm was developed to avoid any scattering of visible light when the helix is not unwound over a certain limit. Planar cells with different FLC layer thickness (16 and 44 μm) have been assembled with helix axis parallel to the glass plates and aligned along the rubbing direction. The ellipticity of the light passing through the cells vs. the electric field was investigated, and a method for evaluating the electrically controlled birefringence via ellipticity measurements has been established. We have found that the FLC cell is an optical retardation layer driven by the electric field, the effective birefringence being proportional to the square electric field. The physical origin of the electrically controlled phase shift of the light passing through the FLC layer has been analysed.     

Untwisting of the helical superstructure in the cholesteric and chiral smectic C*phases of cross-linked liquid-crystalline polymers by strain

It is possible to untwist reversibly the helical superstructure of elastomers with cholesteric and chiral smectic C*phases by using strain. In that way a cholesteric structure can be transformed into a nematic structure and a chiral smectic C*into a smectic C structure. The latter case is especially interesting because a structure without a macroscopic polarization (chiral smectic C*) is transformed into one with a macroscopic polarization (smectic C like arrangement).     

The control of the cholesteric pitch by some azo photochemical chiral switches

A few chiral azo compounds, which undergo reversible photochemical switching, are presented. Of these, the most interesting contain the binaphthyl moiety and belong to the C2 (derivatives 1 and 2) or C1 symmetry group (derivatives 3 and 4). These binaphthyl compounds display intense CD and high beta values. Photochemical switching has profound effects on both the CD and beta values of these compounds; in the case of compound 3, the sign of beta changes upon isomerisation. Compound 2 has, to our knowledge, the highest beta of the switches reported in the literature and also seems the most interesting owing to its fast response to photochemical stimuli. Nematic phases can be transformed into cholesteric phases with reflection bands in the visible region by doping with reasonable amounts of 1 and 2. The reflection colours can be changed reversibly by photoisomerisation of the switches. Thermal reversion of the colourless UV photostationary state to the green isomeric EE state or to intermediate coloured states is temperature dependent. This can allow the thermal history of a sample to be traced.     

An EPR determination of the helix pitch and relative handedness of some induced cholesteric mesophases

The pitch of weakly cholesteric mesophases obtained by dissolving a chiral compound in the nematic liquid crystal MBBA, has been determined by an EPR spin probe technique. The measured values are in excellent agreement with those obtained by the Grandjean-Cano microscopic method. Once a sufficiently large number of EPR simulated spectra have been computed, the experimental procedure for the determination of the pitch is shown to be faster and as reliable as other methods. The handedness of the mesophase can also be easily established by observing the spectral variations which follow the addition of a cholesteric of known handedness to a given sample.     

Temperature dependence of pitch and twist elastic constant in a cholesteric to smectic A phase transition

To understand chirality in cholesteric (Ch) liquid crystals, we performed an experimental study on the Ch-smetic A (SmA) transition of a cholesteric liquid crystal. By studying the reflection spectrum at zero field and at the critical electric field used to unwind the helical structure, we were able to measure the helical pitch P and the twist elastic constant K ²² in the Ch phase. As the temperature was lowered toward the Ch-TGB phase transition, the helical pitch and twist elastic constant diverged. The results support the model that short range SmA forms in the Ch phase. When the results were fitted by power-law temperature dependence, the exponent for P was 0.78 and the exponent for K ²² was 1.36.     

Temperature dependence of pitch and twist elastic constant in a cholesteric to smectic A phase transition

To understand chirality in cholesteric (Ch) liquid crystals, we performed an experimental study on the Ch-smetic A (SmA) transition of a cholesteric liquid crystal. By studying the reflection spectrum at zero field and at the critical electric field used to unwind the helical structure, we were able to measure the helical pitch P and the twist elastic constant K22 in the Ch phase. As the temperature was lowered toward the Ch-TGB phase transition, the helical pitch and twist elastic constant diverged. The results support the model that short range SmA forms in the Ch phase. When the results were fitted by power-law temperature dependence, the exponent for P was 0.78 and the exponent for K22 was 1.36.     

Cholesteric helix inversion: Novel nitro compounds showing unusual changes of the cholesteric helical pitch

We present a homologeous series of liquid crystalline trioxadecalin compounds having a terminal alkoxy chain and a nitro group. The (1S, 3R, 6R,8R)-3-(4'-nitrophenyl)-8-(4'-octoxyphenyl)-2,4, 7-trioxabicyclo [4.4.0]decane 2 c shows a temperature-dependent inversion of the cholesteric helix at lower temperatures. For higher temperatures, the reciprocal helical pitch reaches a minimum, then it increases, tending to a second inversion point just above the clearing point. An additional chiral centre in the side chain leads for nitro compounds 3 to non-mesomorphic behaviour. For the cyano compounds 4, the change in the cholesteric helix is suppressed, for the R configuration, but for the S configuration helical inversion occurs at high temperatures and selective reflection above the transition to the TGB_A phase.     

High precision density studies near the smectic A-nematic tricritical point

We have carried out very accurate density measurements (with a precision of ±5 × 10^-5g cm^-3) near the smectic A-nematic transition in binary mixtures of 4-n-nonyl-4'-cyanobiphenyl (9CB) and 4-n-decyl-4'-cyanobiphenyl (10CB). The transition crosses over from second to first order as the temperature range of the nematic phase decreases. For mixtures with the shortest nematic range the data deviate noticeably from a single power law behaviour. Such a deviation is an indication of the first order nature of the transition. Very good fits to a single power law have been obtained for pure 9CB and the x = 0·04 mixture where x is the mole fraction of 10CB in 9CB. The critical exponent obtained from the power law fitting has enabled us to locate the tricritical point to be very close to x=0·04, which is in agreement with the results obtained previously by high resolution calorimetric [1] and X-ray scattering studies [2].     

Deformed helix ferroelectric liquid crystal display: A new electrooptic mode in ferroelectric chiral smectic C liquid crystals

Abstract

A new electrooptic mode of operation of ferroelectric chiral smectic C liquid crystal displays (LCDs) is proposed and demonstrated. The effect, which is called the deformed helical ferroelectric (DHF) effect, is based on the deformation of the helical structure by weak electric fields. In the unbiased device the smectic layers are arranged in the bookshelf geometry with the helix axis parallel to the electrodes [1]. Systems with a very small pitch (<1 μm) and a large tilt angle are especially well suited for this mode. The key characteristics of DHF-LCDs are: (a) low driving fields (1 V_p-pμm^?1 for maximum contrast); (b) grey scale which is approximately linear with the applied electric field; (c) easy alignment even for thick cells using standard wall-aligning methods; and (d) response times at room temperature of 300 μs.     

Polarization holographic grating recording in the cholesteric azobenzene‐containing films with the phototunable helix pitch

The recording of polarization gratings in films of a cholesteric liquid crystalline polymer with different helix pitch was studied in detail. For this purpose, the cholesteric mixture of the nematic azobenzene‐containing copolymer with a chiral‐photochromic dopant was prepared. The utilization of such mixture has made possible to realize dual optical photorecording in one system, first due to the phototuning of the helix pitch by UV light and second the polarization grating recording process by exposure with polarized visible light. The diffraction efficiency strongly depends on the cholesteric helix pitch and films thickness: the increase of the confinement ratio d/p (where d, film thickness; p, helix pitch) results in growth of the diffraction efficiency. Comparison of the induction of polarization gratings in cholesteric, nematic (copolymer without chiral dopant), and amorphous (nonannealed) cholesteric films revealed that only the cholesteric films were characterized by significant oscillations in the diffraction efficiency signal as well as by the presence of the maximum in the first‐order diffraction efficiency in the initial stage of the grating recording process. It was found that in addition to the polarization grating surface relief gratings (SRGs) were also formed in the studied systems, however, the amplitude of the SRG inscribed in the cholesteric films was lower (～20 nm) compared to the grating amplitude obtained in nematic films (～60 nm). Moreover, increasing helix pitch resulted in a decrease of the SRG amplitude. The obtained experimental data demonstrate the great potential of cholesteric LC mixtures of such type for different applications as photoactive materials for photonics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 773–781     

Synthesis and characterization of chiral smectic C liquid crystalline terpolysiloxanes

A number of tailor-made side chain liquid crystalline terpolysiloxanes, containing chiral cyanohydrin ester, phenyl pyrimidine and fluorinated phenylbenzoate as the side groups, have been synthesized for potential applications as ferroelectric liquid crystal polymers. All the polysiloxanes exhibit the mesomorphic sequence of crystal-chiral smectic C-smectic A-isotropic phases.     

Discontinuous change in the helical pitch of cholesteric liquid crystals by photoisomerization of a chiral azobenzene molecule

This paper describes the discontinuous change in the helical pitch of a cholesteric liquid crystal (ChLC) by means of the photoisomerization of chiral azobenzene molecules under homogenous alignment conditions. A mixture of E44, R811 and Azo was prepared in the ratio 68/28/4, respectively. R811 and Azo have opposite twisting abilities such that they induce right- and left-handed helices, respectively when added to E44. The mixture was injected into a glass cell having a 2 or 5 µm cell gap, and treated for homogeneous molecular orientation. The wavelength of selective reflection from the ChLC was shifted to shorter wavelengths by the trans-cis photoisomerization of Azo. The change in the helical pitch was not only discontinuous, but also dependent on the cell thickness. The discontinuous change in the helical pitch was estimated to be almost the same as the half turn of the helical pitch in each cell gap, and was dependent on the number of helical half pitches in the glass cell. The homogeneous alignment condition affects the photochemical change in the helical structure of the ChLC system.     

Discontinuous change in the helical pitch of cholesteric liquid crystals by photoisomerization of a chiral azobenzene molecule

This paper describes the discontinuous change in the helical pitch of a cholesteric liquid crystal (ChLC) by means of the photoisomerization of chiral azobenzene molecules under homogenous alignment conditions. A mixture of E44, R811 and Azo was prepared in the ratio 68/28/4, respectively. R811 and Azo have opposite twisting abilities such that they induce right- and left-handed helices, respectively when added to E44. The mixture was injected into a glass cell having a 2 or 5?µm cell gap, and treated for homogeneous molecular orientation. The wavelength of selective reflection from the ChLC was shifted to shorter wavelengths by the trans-cis photoisomerization of Azo. The change in the helical pitch was not only discontinuous, but also dependent on the cell thickness. The discontinuous change in the helical pitch was estimated to be almost the same as the half turn of the helical pitch in each cell gap, and was dependent on the number of helical half pitches in the glass cell. The homogeneous alignment condition affects the photochemical change in the helical structure of the ChLC system.     

Orientation of a chiral smectic C elastomer by mechanical fields

It is well known that, with respect to the director, nematic elastomers can be macroscopically aligned by uniaxial mechanical fields. Extending this method to a chiral smectic C elastomer, depending on the experimental set-up either smectic layer orientation or director orientation parallel to the stress axis occurs. In order to align the director and the smectic layers a biaxial mechanical field (e.g. shear field) consistent with the phase symmetry has to be used to achieve a macroscopically uniform orientation of the untwisted smectic C^* structure.