Influence of pressure on the B2I phase transition of a banana-shaped liquid crystal

Employing a phenomenological mean field theory, we analyse the effect of high pressure on the B₂I phase transition properties of a bent-core liquid crystal. The basic idea of the work is to explain the phase transition behaviour of system by assuming that certain Landau coefficients associated with the order parameters coupling terms of the free-energy density expansion are pressure dependent. We observe excellent agreement between the theoretical and experimental results of mesogen PHDBB and that the B₂I transition remains first order even at the elevated pressures.     

High-pressure phase transitions in liquid crystals

Simultaneous measurements of the rate of heat evolution and changes of the mechanical variable of a transformation such as volume or pressure, performed in a p-V-T controlled scanning calorimeter have been applied to investigations of phase transitions in liquid crystals. In the instrument, the phase transitions can be induced by a controlled change of pressure, volume or temperature under isothermal, isobaric or isochoric conditions respectively. The present investigations have ben performed on 4-n-penthyl-penthylthiol-4-decycloxybenzoate which demonstrates in the liquid crystal state a nematic and three smectic phases

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Zusammenfassung In einem p-V-T-kontrollierten Scanning Kalorimeter wurden zur Untersuchung der Phasenumwandlungen in Flüssigkeitskristallen simultane Messungen der Geschwindigkeit der Wärmeentwicklung und der Veränderungen von mechanischen Größen von Umwandlungen, wie z.B. von Volumen oder Druck durchgeführt. In diesem Gerät kann die Phasenumwandlung durch eine kontrollierte Veränderung von Druck, Volumen oder Temperatur unter isothermen, isobaren oder isochoren Bedingungen ausgelöst werden. Vorliegende Untersuchungen wurden an 4-n-Pentyl-phenylthiol-4-dezyloxybenzoat durchgeführt, welches im Flüssigkristallzustand eine nematische und drei smektische Phasen aufweist.

     

Halogenation in achiral liquid crystals: terminal and linking substitutions

The effect on the physico-chemical properties of achiral liquid crystals of introducing halogen atoms into their terminal and linking groups is discussed and rationalized in terms of existing theories; a comparison is made with the corresponding hydrogenated and other well-known groups.     

Nitro substitution in achiral calamitic liquid crystals

This review examines in some detail the effect of terminal and lateral nitro substitutions in achiral calamitic liquid crystals on their physico-chemical properties. The results of this study are compared with those obtained for other groups, and are rationalized in terms of existing theories.     

Polarisation-dependent dielectric processes in ferroelectric liquid crystals

The behaviour of dielectric relaxation process has been investigated in four ferroelectric liquid crystal (FLC) materials having different spontaneous polarisation (Ps) values. Ps effect on the permittivity in four different FLCs has been carried out in highly anchored sample cells around ~8 μm thick. It has been found that the main contribution to the dielectric permittivity in chiral Smectic C (SmC*) phase is due to Goldstone mode (GM) and partially unwound helical mode (p-UHM). In higher PS value FLC materials, the p-UHM process is found to dominate the dielectric properties. It has also been observed that p-UHM process is highly dependent on the probing ac voltage and temperature, whereas GM is found to be weakly dependent of probing voltage and temperature in SmC* phase of all the studied FLC materials. The influential contribution of p-UHM has exhibited the dielectric properties in its intrinsic frequency range making the materials suitable for futuristic display and photonics devices.     

Columnar phases of achiral vanadyl liquid crystalline complexes

Two liquid crystalline vanadyl complexes have been studied by frequency domain dielectric spectroscopy over the range 10 mHz to 13 MHz. The materials exhibit two or three columnar phases denoted Col_ro, Col_rd, and Col_hd that were identified by X-ray diffraction. In the higher temperature Col_rd phase, a relaxation process in the kHz range is observed that is attributed to the reorientation about the molecular short axis. A pronounced dielectric relaxation process shows up in the low temperature Col_ro phase at hertz and sub-hertz frequencies. This slow relaxation is assigned to reorientation of the molecular dipoles within the polar linear chains, which are aligned along the column's axis. Triangular wave switching studies at low frequency reveal processes inside the Col_ro phase which are most probably due to ionic/charges relaxations but a ferroelectric switching for an achiral discotic system cannot be ruled out completely. Below the Col_ro phase there is an orientationally disordered crystalline Cr_x phase with disordered side chain dipoles. A dielectric relaxation process connected with the intramolecular relaxation of the alkoxy side chains, similar to the beta-process of polymers, has been found in the lower temperature Cr_x phase.     

Holographic recording in chiral and linear isomers of single-component phototropic liquid crystals: an experiment and theoretical approach

Phototropic liquid crystals (PtLC) comprising one component are a new class of liquid crystals (LC) which due to the phenomenon of photochemical phase transition are of special interest, especially in view of their potential applications in photonic devices. So far, however, only a little attention has been paid to these materials. In this paper, we discuss holographic recording in chiral and linear single-component PtLCs from the family of 4-alkyl-4?-alkoxyazobenzene and we develop the one-dimensional mathematical model describing the formation of the diffraction grating. The grating formation process and its dynamics, resulting from the photoinduced isotropic-to-nematic phase transition, have been described by the mechanism that assumes the formation and growth of the liquid-crystalline domains of different sizes induced by the sinusoidally modulated Gaussian light intensity distribution. We show that the model is based on one parameter, that is the incubation time which can be easily obtained experimentally and which can be used for the fitting of the experimental data. Reporting new PtLCs materials and the model that describes the processes of holographic recording in these types of materials can be useful in the design of new phototropic LC materials and for optimisation of the experimental conditions.     

Simple and accurate ac calorimeter for liquid crystals and solid samples

We have designed, built and calibrated a microcomputer-controller automated a.c. calorimeter for liquid crystals and solid samples, in the temperature range from 30 to 250°C, in which we enhance several features of previous ones reported in the literature. We have incorporate the lock-in amplifier model 5302 from EG&;G in our set-up, which permits to extend the frequency range to 1 mHz. This allows the performance of suitable frequency sweeps in order to choose the optimum operating frequency for low thermal conductivity materials. The calorimeter has been calibrated with the 8OCB liquid crystal compound. The resolution obtained forC _p values was better than 0.1% and the absolute erroer around 5%. As applications, we show the ferroelectric transition of the triglicerine sulphate (TGS), the Nematic-Smetic A transition of the 8OCB and a study in a binary system of ferroelectric liquid crystals, SCE9-SCE10.     

Synthesis of achiral four-ring unsymmetrically substituted toluene derived liquid crystals with a polar end group

Achiral four-ring unsymmetrically substituted toluene-derived liquid crystals have been designed and synthesised by known and straightforward methods. All these compounds exhibit nematic phase over wide temperatures.     

Synthesis and characterisation of reactive liquid crystals containing an azo group

A new series of liquid crystal (LC) monomers – not only contain a double bond but also contain an azo group – were designed and synthesised. The length of side groups in the LC monomers containing azobenzene ester varied from 1 to 2 methylene units, and the length of the substituted groups in the main chain varied from 1 to 3 methylene units. The molecular structures of the intermediates and target compounds were confirmed by Fourier transform infrared, ultraviolet and visible spectrum and nuclear magnetic resonance (NMR) spectroscopy. The thermal phase behaviour of the LC monomers was investigated by polar optical microscopy coupled with hot stage and differential scanning calorimetry (DSC). In this paper, the effect on the LC zone with the substituents were investigated, and with the increased methylene of main chain, the melting point and the phase transition temperature of the substance will be lowered and LC regions will be narrower.     

Synthesis and mesomorphic properties of three-benzene-ring-containing banana-shaped liquid crystals

A homologous series of three-benzene-ring-containing banana-shaped compounds, N,N-bis(4-alkylcarbonyloxybenzylidene)benzene-1,3-diamine, were synthesised by esterifying aliphatic acids with the three-benzene-ring bent core 1,3-phenylene-bis(4-hydroxybenzylideneamine). As the number of carbon atoms in the aliphatic acids increased from 1 to 12, 12 novel banana-shaped compounds resulted with increasing lengths in their terminal tails. The mesomorphic properties of this homologous series of three-benzene-ring-containing banana-shaped compounds were characterised by means of polarised optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical studies. Our results have demonstrated that this series of banana-shaped compounds can form mesophases, although each of their bent cores contains only three benzene rings.     

Thermal tuning band gap in cholesteric liquid crystals

The phase of a liquid crystal (LC) changing from a nematic phase to a cholesteric (Ch) mesophase is achieved by adding different ratios of chiral dopants S811. By studying the transmission spectrum, we are able to measure the helical pitch in cholesteric phase. The pitch in the mixtures of nematic E7 and chiral dopants S811 as a function of the concentration of the dopant and temperature is investigated. The sensitivity of the selective reflection notch of the cholesteric phase to the thermal tuning depends strongly on the ratios of the chiral dopants. It reveals that the influence of temperature is more profound for those cholesteric liquid crystals (CLCs) which exhibit smectic A (SmA) at lower temperatures. When fitted using Keating's formula, the helical pitch calculated from our experimental results lies on the predicted curve. Optimised ratios of the mixture CLCs for the optimised reflection band with the specified wavelength ranging from 467 nm to 2123 nm are suggested.     

Ethylenedioxythiophene as a novel central unit for bent-core liquid crystals

We have discovered that ethylenedioxythiophene (EDOT) can be used as a central unit for the synthesis of bent-core liquid crystals (BC LCs). Two series of EDOT-based BC LCs are prepared via Sonogashira coupling reaction. The mesophase behaviour of all the compounds was characterised using a combination of polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. EDOT-based three-ring compounds were found to be nonliquid crystalline, while all the four derivatives of five-ring series, including a branched alkoxy chain derivative, display enantiotropic nematic phase over wide temperature range. The bent angle of these compounds is about 153°, which falls in between typical rod-like and banana liquid crystals. The transition temperature of branched alkoxy chain compound is lower than straight alkoxy chain compounds. The detailed XRD investigations of all the mesogens corroborate the presence of nematic phase.     

Non-covalent intermolecular interactions of colloidal nematic liquid crystals doped with graphene oxide

Graphene oxide (GO) was doped to eutectic uniaxial nematic liquid crystals (NLCs) (E_5CN7) with different percentages to improve the physiochemical properties of NLCs effectively. GO shifts the N-I phase transition temperature to higher values. It has been observed that increasing GO concentration up to 0.75% increases the N-I phase transition temperature substantially while further increase of GO concentration results in an inverse trend. The GO/E_5CN7 non-covalent interactions change the N-I phase transition. The contribution of several terms such as anchoring and polarisation effects on N-I phase transition was quantified as well. The results suggest that the size is an important contributor to GO and liquid crystal interaction. The results show that E_5CN7@GO composites may act as promising candidates to enhance the efficiency of room temperature devices.     

Azeotropic-like (congruent melting) phenomena of lamellar liquid crystals

The binary system of water and didecyldimethylammonium bromide (DDeAB), having a double hydrocarbon chain, was found to exhibit exhibit an azeotropic-like phase transition from lamellar liquid crystal to micellar solution. That is, the maximum limiting value of temperatures where the present system is allowed to exist in a lamellar liquid crystal corresponds to the socalled azeotropic point (AZP) or congruent melting point. At this temperature, the compositions of the liquid crystal and micellar solution phases become identical. Upon addition of a small amount of NaBr, the AZP shifts to a high temperature, but the point disappears above 0.375 wt% NaBr in water. The AZP is also increased by adding cholesterol. On the other hand, the transition enthalpies at AZPs are extremely small and almost constant, even if NaBr and cholesterol are added. The sharp DSC peak is observed in the presence of salt, whereas it is broad in the presence of cholesterol. It is considered that salt induces a closely packed state of the liquid crystal phase. Although cholesterol also has an ordering effect on the surfactant aggregates its hydrophobic property increases the phase transition temperature. The phase transition occurs due to a packing change of the hydrocarbon chains of DDeAB molecule from the lamellar to micellar states. The correlation between the movement of AZP and the phase behavior in the presence of salt is also discussed.     

Study of the electrocaloric effect in ferroelectric liquid crystals

ABSTRACT

Electrocaloric effect (ECE) in two ferroelectric liquid crystalline (FLC) materials has been evaluated by mean of two indirect characterization methods: the photopyroelectric (PPE) technique and the polarization current reversal one. The obtained results show a good correspondence of the adiabatic temperature change associated with the ECE evaluated from both methods. This validates the possibility to use the PPE technique to investigate the ECE in FLCs. This study also demonstrates that FLCs can be used as electrocaloric material. More particularly, it shows that as for their solid homologous, liquid crystals displays more pronounced ECE in the vicinity of a first order transition than that measured near to second-order one.     

Four ring achiral ferroelectric liquid crystals of 1,2,4-oxadiazoles: synthesis and characterisation

A novel series of four-ring achiral ferroelectric liquid crystals containing 1,2,4-oxadiazole cores with unsymmetrical substitutions at C-3 and C-5 positions are synthesised and characterised. A fluoro substituted biphenyl moiety is prepared by Suzuki coupling reaction and is directly attached to the oxadiazole core at the C-5 position for the first time in the literature. An octyl benzoate is attached to the oxadiazole core at the C-3 position of it. All the compounds exhibit polar smectic (B₂) mesophases with ferroelectric switching along with the orthogonal smectic-A mesophases. These compounds possess high mesomorphic thermal ranges of polar smectic phases and are towards the ambient temperatures. The influence of a more electronegative fluorine substituent on the electron rich biphenyl moiety (at the C-5 position) of the oxadiazole core is analysed for the prevalence and abundance of polar smectic (ferroelectric) mesophases.     

Cholesteric star-shaped liquid crystals induced by a maltose core: synthesis and characteristics

Three esters of maltose (A1–A3) with 4–(4–(alkoxybenzoyloxy)phenoxy) –6–oxohexanoic acid (b1–b3) side-arms have been synthesised. All the maltose derivatives were laevo-rotationary, unlike their parent cores. The side arm b1 did not display liquid crystalline (LC) properties, and b2 and b3 displayed thermotropic nematic LC properties. The star-shaped compound (SSC) A1 with b1 side-arms did not display a mesomorphic phase. Unlike the nematic schlieren texture provided by side-arms b2 and b3, the star-shaped liquid crystals (SSLC) A2 and A3 displayed Grandjean and oily texture in the cholesteric phase. The results suggest that the LC properties of the side-arms have an important influence on the formation of LC properties in an SSC, and that the maltose core is important in determining the mesomorphic phase type. In other words, the SSC displayed LC properties only when the side-arms were also LC, and the maltose core induced a cholesteric phase in the SSLC with nematic side-arms. The mesomorphic regions for A2 and A3 were 39.1 and 53.7°C during the heating cycle and 63.8 and 107.0°C during the cooling cycle, respectively. The longer terminal chain rendered the mesomorphic region broader.