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。     

Design and characterization of hydrogen bonded ferroelectric liquid crystals: A study of light modulation in nematic and smectic orderings

A novel series of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been isolated. Phase transition temperatures obtained by differential scanning calorimetry (DSC) and textural observations elicited by polarizing optical microscope (POM) studies are discussed. Phase diagram is constructed from the above data. Salient feature of the present work is observation of a light modulation due to field induced transitions (FiT) in nematic and smectic C* phases. Tilt angle measurements in various FiT of smectic C* phase are discussed. One of the mesogens in nematic phase behaves like an optical modulator; helical pitch measurements support the above observation.     

Critical behaviour of the smectic A*–C* phase transition and electroclinic effect of ferroelectric liquid crystals with terphenyl rigid core

The SmA*–SmC* phase transition was studied by measuring the temperature and electric field dependences of the optical tilt angle, the electric polarisation and the dielectric spectra collected in a wide frequency range. Critical behaviour of the phase transition was analysed by varying the length of the fluorinated part of the alkyl terminal chain and by differing fluorine substitution in the terphenyl core. Both tilt and polarisation show tricritical mean-field behaviour for all homologues with n?>?2. Almost all coefficients that describe the SmA*–SmC* transition in the frame of the Landau theory were derived for homologue series. Double fluorine substitution in the central ring of the core seems to promote the ‘de Vries'-type smectic A*–C* phase transition with a little layer shrinkage. These well correspond with the lower tilt angle and smaller changes of the birefringence at the phase transition compared to the other homologues.     

Study and characterization of the smectic X* phase in binary mixtures of thermotropic double hydrogen bonded ferroelectric liquid crystals

Thermotropic double hydrogen bonded ferroelectric liquid crystals (DHBFLCs) composed of N-carbamyl-L-glutamic acid (CGA) and p-n-alkyloxy benzoic acids (BAO) have been investigated. Variation in the molar proportion of X and Y (where X = CGA + 5BAO and Y = CGA + 6BAO, CGA + 7BAO, and CGA + 8BAO) composed of three series yielded 27 binary mixtures. Optical and thermal properties of these mixtures are meticulously studied in the present article. A novel smectic ordering, namely smectic X*, is observed in all the three series. The aim of the investigation is to obtain an abundance occurrence of smectic X* and hence the proportions of the binary mixtures are so chosen that the preamble task is accomplished. Phase diagrams of three series are constructed from the data obtained from polarizing optical microscope (POM) and differential scanning calorimetry (DSC) studies. Odd–even effect, order of the phase transition, thermal stability factor, thermal equilibrium, and optical tilt angle are also premeditated.     

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     

The properties of ferroelectric compound (S)-(+)-4-(1-methylheptyloxycarbonyl)phenyl 4′-(4-cyanoacetoxybut-1-oxy) biphenyl-4-carboxylate and its ability of an antiferroelectric phase induction in mixtures

Phase transitions and ferroelectric properties of (S)-(+)-4-(1-methylheptyloxycarbonyl)phenyl 4′-(4-cyanoacetoxybut-1-oxy)biphenyl-4-carboxylate will be described in this article. This compound exhibits the synclinic smectic C* phase and it has the ability to induce an antiferroelectric phase in mixtures with the other ferroelectric compounds. New systems with induced antiferroelectric phase and their properties are presented.     

Dielectric and calorimetric studies on 1BC1EPOPB feroelectric liquid crystal having a large spontaneous polarization

Experimental investigations on the ferroelectric liquid crystal, R-4′(1-butoxycarbonyl-1-ethoxy) phenyl 4-(4-octyloxy phenyl) benzoate (1BC1EPOPB) of large spontaneous polarization (P _S(+) = 240?nC?cm^?2), using dielectric and calorimetric techniques, are reported. The temperature range of 25.0–125.0°C has been chosen for dielectric measurements. Dielectric dispersion studies are carried out in the temperature range 45.0–75.0°C and in the frequency range 2?Hz to 2?MHz for the smectic A, smectic C* and smectic X phases. A new phase called ‘smectic X’ has been found around 56.3°C. The transition temperatures identified by the dielectric dispersion studies for different phases and those given by DSC techniques are in close agreement.     

Thermodynamic,optical and switching parameters of a ferroelectric liquid crystalline material having SmA*-SmC*-SmBh* phase sequence

Thermodynamic and electro-optical characterization of a ferroelectric liquid crystalline material, namely ((S) (+) 4-(1-methylheptyloxy) phenyl 4′-octyloxybiphenyl-4-carboxylate) possessing paraelectric SmA*, ferroelectric SmC*, hexatic SmB_h* and SmI* phases has been carried out. Phase identification has been done by optical and thermodynamic studies. Switching parameters viz. spontaneous polarization, switching time and rotational viscosity have been determined. The spontaneous polarization has been found to increase with decreasing temperature in SmC* phase. The switching time is found of the order of few milliseconds.     

Design, synthesis and characterization of a linear hydrogen bonded homologous series

A linear hydrogen bonded liquid crystalline homologous series has been synthesized and characterized. Hydrogen bond is formed between p-n-dodecyloxy benzoic acid and various p-n-alkyl benzoic acids whose alkyl chain vary from octyl to ethyl. Synthesized complexes are characterized by FTIR, ¹H NMR and ¹³C NMR studies for inferring the formation of hydrogen bonds. Polarizing Optical Microscopy (POM) and DSC studies reveal various mesophases and their corresponding transition temperatures along with respective enthalpy values. All the seven synthesized complexes exhibit rich liquid crystalline mesomorphism. A new phase namely smectic X has been observed in five of the complexes with a narrow thermal range. This phase has been characterized by optical textural, DSC, tilt angle and helicoidal pitch studies. Smectic X is sandwiched between traditional smectic C and re-entrant smectic C (designated as C_R) phases. Homeotropic transition in nematic phase is observed in all the mesogens and thus these materials can be used as thermally controlled optical shutters. Tilt angle in smectic C, smectic X and smectic C_R phases have been experimentally elucidated for all the mesogens.     

The Phase Transitions from Chiral Nematic Toward Smectic Liquid Crystals

A Chen-Lubensky energy is used to investigate phase transitions from chiral nematic to smectic C* and smectic A* liquid crystal phases. We consider a liquid crystalline material Ω confined between two parallel plates, where the dimensions of Ω are assumed to be large relative both to the width of a smectic layer and the material’s chiral pitch. We take boundary conditions so that the smectic phase melts at the plates’ surfaces and prove the existence of energy minimizers in an admissible set consisting of order parameters and molecular directors . Then under the physically observed assumption that the Frank elasticity constants become large near a phase transition, we establish estimates for the transition region separating phases. In particular we derive analytic estimates proving that chirality lowers the transition temperature regime above which minimizers are nematic and below which minimizers are in a smectic phase.Research supported by NSF grants DMS-0306516 and DMS-0456286.     

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.     

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.     

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.     

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

A homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IV_n), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1–10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.     

Optical modulation in nematic phase of halogen substituted hydrogen bonded liquid crystals

A series of halogen-substituted hydrogen-bonded liquid crystalline complexes have been designed and synthesised. A successful attempt has been made to form complementary hydrogen bonding between the dodecyloxy benzoic acid (12BAO) and halogen-substituted benzoic acids and the physical properties exhibited by the individual complexes are studied. The complexes obtained are analysed by polarising optical microscope (POM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and dielectric studies. The formation of complementary hydrogen bond is confirmed through FTIR spectra. An interesting feature of this series is the observation of a field-induced transition (FiT) in nematic phase. Another interesting phenomenon is the observation of a new smectic X phase (worm-like texture) in all the synthesised complexes. Dielectric relaxation studies in the smectic C phase of these hydrogen bonded complexes along with the Arrhenius and the Cole–Cole plots are discussed. Optical tilt angle in smectic C phase and the corresponding fitted data analysis concur with the Mean field theory prediction.     

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.     

Experimental observation of multicritical behaviors in pressure-temperature diagrams of pure compounds with twist grain boundary phases

In order to study critical behaviors of pure compounds anticipated by Renn and Lubensky's theoretical calculations, high-pressure experiments have been performed on six tolan series homologous to the 3-fluoro-4-[(R) or (S)-methylheptyloxy]-4'-(4"-alkoxy-2",3"-difluorobenzoyloxy), which exhibit the twist grain boundary (TGB(A) and TGB(C)) mesophases. Measurements were carried out by thermobarometric analysis. Six pressure-temperature phase diagrams are determined. The studies establish the existence of multicritical points twisted-smectic-C (S*(C))-TGB(C)-TGB(A), TGB(C)-TGB(A)-cholesteric nematic (N*) and S*(C)-TGB(C)-N* for single component systems in pressure-temperature (P-T) phase diagrams. Our results also show that a pressure increase has the same effect on the (P-T) phase diagrams as a decreasing number of carbon atoms in the aliphatic chain; then pressure change can have the same effects on intermolecular interactions as those observed when shortening the molecular length. The existence of transition lines with negative slope values was also found. The experimental results are in qualitative agreement with the model proposed by Renn and Lubensky.     

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.