‘Guest–host’ effect in liquid crystal mixtures

The most important goal of our research is to show the influence of the ‘guest’ (bent-core mesogen, 1,3-phenyldicarboxylatebis{4-[(4-octylbenzoyl)sulphanyl]phenyl} [IFOS8], banana-shaped liquid crystal [BLC]) on the ‘host’ (calamitic liquid crystal [CLC], (S)-(+)-1-methylheptyloxybiphenyl-(4-n-octylphenyl)thiobenzoate [MHOBS8]), on the stability and the destabilization of the antiferroelectric B2 and the ferroelectric smectic C* (SmC*) phases, and change of the temperature ranges of other phases in the binary liquid crystal mixtures. This work is focused on polymorphism of three new binary liquid crystal mixtures, exhibiting a ‘guest–host’ (guest liquid crystal–host liquid crystal [GH-LC]) effect. MHOBS8 has, among others, a ferroelectric SmC* phase, and IFOS8 assumes the B2 phase with antiferroelectric properties. The observed properties of the mixtures, such as variation of the phase transition temperatures, spontaneous polarization, tilt angle and switching time, are characteristic of a ‘guest–host’ mixture. The influence of BLC on the character of the interactions within the CLC host is discussed, with particular attention paid to electro-optical properties of the GH-LC mixtures.     

Investigation of the Kerr effect and third-order susceptibility constants in a nematic liquid crystal

In this paper, the static Kerr effect was investigated for the W-1680 at temperatures above the nematic-isotropic transition temperature and compared with 9CHBT. We experimentally measured the electro-optical Kerr constant and the pre-transitional behavior. The Kerr law has been confirmed and the variation of the inverse Kerr constant, with a temperature above the smectic-isotropic transition temperatures, were determined. The linear dependence of (T − T*)^− 1 on the Kerr constant is found to be in good agreement with the predications of the Landau-De Gennes model. Additionally, the temperature dependence of third order susceptibility has been studied. This value for these samples will reduce when the temperature increases.     

Orthoconic antiferroelectric liquid crystals containing biphenyl,terphenyl, or naphthyl mesogenic unit

Three homologous series of orthoconic (45 degree tilt) antiferroelectric liquid crystals containing either naphthyl or terphenyl groups as mesogenic unit have been synthesized and their mesomorphic behaviour investigated by DSC and polarized light microscopy, and their properties discussed. X-ray diffraction studies have shown the presence of a de Vries-type smectic A phase which does not exhibit a layer shrinkage on transition to the ferroelectric smectic C phase. Mixtures of the new materials have been formulated and their electro-optical properties investigated for their use in surface stabilized orthoconic antiferroelectric liquid crystal (SSOAFLC) devices     

Dielectric spectroscopy of the SmQ* phase

Liquid crystal possessing two biphenyl moieties in the molecular core and lateral chlorine substitution far from the chiral chain has been studied by dielectric spectroscopy. On cooling from the isotropic phase, the material possesses the frustrated smectic Q* (SmQ*) and SmC_A* phases. It has been confirmed by dielectric spectroscopy that the SmQ* phase can be related to the SmC_A* anti-ferroelectric phase. However, only one relaxation process has been observed in the SmQ* phase, while in the SmC_A*, two relaxations are clearly detectable. It seems that the mode found in the SmQ* can be connected with high-frequency anti-phase mode observed in the SmC_A* phase. Its relaxation frequency is similar to P_H relaxation frequency, but is weaker. The same relaxation has been observed even a few degrees above the SmQ*–Iso phase transition. Another explanation for the mode detected in SmQ* and isotropic phases can be molecular motions around short molecular axis.     

西佛碱型液晶化合物相变过程中分子排列方式变化的拉曼光谱研究

用变温拉曼光谱对相变过程的研究表明,液晶化合物的初始晶态与熔融后缓慢降温得到的晶态并不吻合,两个状态下分子尾链的构象及刚性核部分的构象不同导致分子的聚集状态不同。西佛碱型液晶化合物VO10相变过程中,在晶态到液晶态相转变过程中,烷氧基尾链链内构象发生突变,同时有序性降低,刚性核部分两个苯环之间的二面角在相变点时发生明显变化,二面角加大。     

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.     

Synthesis and phase transition studies on non-symmetric liquid crystal dimers: N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)-benzylidene)-4-chloroanilines

A new series of non-symmetric liquid crystal dimers N-(4-(n-(4-(benzothiazol-2-yl)phenoxy)alkyloxy)benzylidene)-4-chloroaniline containing benzothiazole and benzylideneimine units connected by a flexible alkyl spacer, –(CH₂) _n –, with n ranging from 4 to 12 in even parity have been prepared. All five members of this homologous series exhibit an enantiotropic nematic phase. The compounds with greater n of 8–12 exhibit both nematic and smectic phases upon cooling. A notable feature among this series is that for the member with n?=?10, the smectic–nematic transition is also present. The nematic–isotropic transition temperatures and associated entropy changes with respect to all compounds in this series exhibit a dramatic dependence on the length of the flexible spacer. A comparison of the transitional properties of this series with those of α-(4-benzylidenechloroaniline-4′-oxy)-ω-[4-(thiophene-2-carboxyl)benzylideneaniline-4′-oxy]alkanes reveals that replacing benzothiazole moiety at one side of the flexible alkyl spacer reduces the nematic–isotropic transition temperature.     

Dielectric properties of LC mixture with induced antiferroelectric phase

Mixture of two liquid crystalline components exhibits the antiferroelectric phase in a broad temperature range at room temperatures, though the two components separately do not show an antiferroelectric phase in a temperature range applied. The dielectric spectroscopy technique combined with measurements of the selective light reflection was used for identification and characterization of the phases and subphases existing in the mixture. In the SmC*_A phase, the low frequency mode characteristic of antiferroelectric phase has been detected. In the broad temperature range between SmC*_A and SmA* phases, no relaxation mode has been detected. The soft mode registered near the phase transition to SmA* phase follows the Curie-Weiss law.     

Dynamic mechanism of the ferroelectric to antiferroelectric phase transition in chiral smectic liquid crystals

The temperature-induced phase transition between the chiral smectic phases, antiferroelectric (smectic-C(A)*) and ferroelectric (smectic-C*), is found to occur through solitary wave propagation. We measure the free energy, which shows a double well shape in the entire SmC(A)* temperature range and the global minimum is found to shift from the antiferroelectric order to the ferroelectric order at the transition temperature. However, any significant supercooling is not observed and the transition cannot be described by the first order Landau-de Gennes theory, where the double well potential exists only in a narrow range of temperatures. This implies that the SmC(A)*-SmC* transition can occur only nonhomogeneously through the solitary wave propagation which overcomes the high energy barrier between the two minima.     

酯类铁电液晶的相变和构型研究(英文)

：本文对酯类铁电液晶的相变和构型进行了研究和评述。它包括固相 近晶Ｃ,近晶Ｃ 近晶Ａ相变的性质,一级、二级相变的判据,固相 近晶Ｃ相变的临界弛豫,顺式、反式的构型转变和新相分析。     

Surface-surface interaction in smectic liquid crystal films

Null transmission ellipsometry was employed to study the field induced transition of the surface arrangements in freestanding films of smectic liquid crystals. The interlayer interaction between the two surfaces obtained from the threshold voltage for the transition is found to be antiferroelectric and is quasilong ranged. The possible microscopic origins of the measured interaction and its relevance to the interlayer interaction in antiferroelectric liquid crystal materials are discussed.     

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.     

Phase diagram of transitions from an isotropic phase to nematic and smectic (uniaxial,biaxial) phases in liquid crystals with achiral molecules

The phase diagrams of transitions from an isotropic phase to nematic and smectic phases are investigated within a simple phenomenological model of the Landau thermodynamic potential. The conditions of the isomorphic phase transition between two uniaxial smectic phases and the direct transition from the isotropic phase to the uniaxial and biaxial smectic phases are determined. The behavior of the order parameters is described along different thermodynamic paths. The theoretical results are discussed using the example of liquid-crystal phases in compounds with banana-shaped achiral molecules.     

Comparative study of liquid-crystalline ordering in a monomer,linear polymer,and graft copolymer by the photon transmission technique

The photon transmission technique was used to study the phase transitions of a liquid crystalline acrylate monomer, 6-(4-cyanobiphenyl-4′oxy)hexyl acrylate (LC6), its homopolymer (PLC6) and its graft copolymer (GLC6) with polytetrahydrofuran grafts. The phase transitions were also confirmed by DSC and polarizing microscopy. We observed the phase transition sequence isotropic–nematic–smectic A–smectic C in the LC6 monomer. In PLC6 and GLC6 polymers, the nematic and smectic A phases appear dominant. The apparent nematic–smectic A transition is of first order in PLC6 and of second order in GLC6, with the transition temperature remaining the same. The effects of quenched random constraints introduced in GLC6 are consistent with the theory of quenched random interactions. The critical exponents were also evaluated.     

Phase diagram involving the mesomorphic behavior of binary mixture of sodium oleate and orthophosphoric acid

The present investigation deals with the binary mixture of two non-mesogenic compounds, viz. sodium oleate (Naol) and orthophosphoric acid (H₃PO₄) which exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixtures with concentrations ranging from 10% to 90% Naol in H₃PO₄ exhibit SmA, SmC, SmE and SmB phases, sequentially when the specimen is cooled from its isotropic phase. Physical properties, such as ultrasonic velocity, adiabatic compressibility and molar compressibility, show anomalous behavior at the isotropic to mesosphase transition.     

Design,synthesis and characterization of a linear hydrogen bonded homologous series exhibiting reentrant smectic C ordering

Design, synthesis and characterization of seven linear hydrogen bonded liquid crystal complexes derived from mesogenic p–n-decyloxy benzoic acid and p–n-alkyl benzoic acids designated as 10OØn (where n varied from ethyl to octyl) are reported. FTIR studies confirm the hydrogen bond formation in all these complexes. The phase transition temperatures and their corresponding enthalpy values are experimentally deduced from Differential Scanning Calorimetry (DSC) studies. POM and DSC data are further utilized for the construction of 10OØn phase diagram. Two Odd–even effects have been evinced, one in enthalpy values and the other in corresponding transition temperatures across the isotropic to nematic phase transition. An interesting result is the observation of re-entrant smectic ordering, designated as smectic C_R in three higher ordered mesogens. A new smectic ordering, smectic X, has been observed which is sandwiched between traditional smectic C and re-entrant smectic C_R. Magnitudes of optical tilt angle in smectic C, smectic X and smectic C_R are experimentally found to attain saturation with decrement of temperature in the corresponding phase. The occurrence of smectic X and smectic C_R are discussed with relation to the molecular chemical structure. The optical filtering action in smectic C and re-entrant smectic C_R phases have been analyzed.     

Low frequency dielectric spectroscopy of two room temperature chiral liquid crystal mixtures

Dielectric spectroscopy of two room temperature chiral liquid crystal mixtures (W-96 and W-97) have been carried out in the frequency range of 100?mHz–10?MHz. Low frequency dielectric relaxation modes corresponding to collective behavior of molecules (Goldstone- and soft-modes) in the SmC* phase have been found to be masked by the ionic conductance. Two slow modes of dielectric relaxation due to the ionic conductance have been detected (below 15?Hz) in planar-aligned samples. It has been observed that the effect of ionic conductance decreases with the number of thermal annealing cycles on the materials. With large number of thermal annealing cycles it has been possible to wipe out the effects of ionic conductance and then to detect other weak modes of dielectric relaxation which are otherwise masked.     

Effect of density variation on the Sm A–I phase transition properties

Based on a thermodynamic model, we investigate how the density variation influences the smectic (Sm A)–isotropic (I) phase transition. We find that the density variation shifts the smectic A–isotropic transition temperature, however, first-order nature of the transition remains the same. Here, we also examine the effect of high pressure on the thermodynamic quantities. The present analysis shows that the pressure strongly influences the enthalpy and density step at the clearing transition. The pressure dependence of the thermodynamic properties is incorporated through the pressure dependent second Landau coefficient and the coefficients which couple the nematic and smectic order parameters to the density. We find a close agreement between theoretical and experimental results. Furthermore, we discuss the implications of the results for achiral liquid crystals.     

Smectic-A*-smectic-C* transition in a ferroelectric liquid crystal without smectic layer shrinkage

The smectic layer spacing of a nonfluorinated ferroelectric liquid crystal (FLC) compound with almost no shrinkage and only minor tendency to form zigzag defects was characterized by small angle x-ray diffraction. The material lacks a nematic phase. The smectic-A*-smectic-C* phase transition was studied by measuring the thermal and electric field response of the optical tilt and the electric polarization. These properties are described very well by a Landau expansion even without introduction of a higher-order Theta(6) term. This result suggests a pure second-order phase transition far from tricriticality and differs considerably from the typical behavior of the A*-C* transition in most FLC materials.