Thermodynamics of activated phase transitions of 8CB: DSC and MC calorimetry

The present paper reports the heating rate effect on the phase transitions of a pure liquid crystal octylcyanobiphenyl (8CB) with use of Differential Scanning Calorimetry (DSC) and Modulation Calorimetry (MC) techniques. The DSC runs were taken at various temperature ramp rates from 20 to 0.5 K/min for heating and cooling scans. Well-defined endothermic/exothermic peaks were found at the melting/crystallization, smectic-A to nematic (SmA-N), and nematic to isotropic (N-I) transitions on heating/cooling scans, respectively. All transitions shift in temperature significantly with different ramp rates. The temperature shift of C(p) peaks between heating and cooling scans indicates the order of the transitions. In addition, all transitions follow an Arrhenius behavior. The activation energy of a transition increases as the total energy involved in the transition decreases. The respective enthalpy and entropy change of each transition provides information on the Gibbs free energy. The significance of the results is discussed in terms of the order of transitions. A comparative analysis of MC and DSC techniques highlights the significance of the two techniques. MC is a practicable tool for observing the phase dynamics whereas DSC is a good tool for studying the rate kinematics of the transitions.     

Nematic to smectic-A phase transition in mixture of liquid crystal and nonmesogenic impurities: existence of tricritical point

Experiments on the mixture of liquid crystals and nonmesogenic impurities showed the significant role of nonmesogenic impurities on the nematic–smectic-A phase transition. Using both Flory–Huggins theory of isotropic mixing and Landau–de Gennes theory, we present a phenomenological theory that discusses the role of such impurities on the nematic–smectic-A phase transition in a mixture of smectic liquid crystal and nonmesogenic impurities. We discuss the impact of nonmesogenic impurities on the order parameters, Frank elastic constants (splay and bend) and transition temperature of the nematic–smectic-A phase transition. Our theoretical results show that there exists a tricritical point for which the second-order nematic–smectic-A phase transition becomes first order at a tricritical point by increasing the concentration of nonmesogenic solute. We find a remarkable agreement between theoretical and experimental results.     

Nucleation of filaments of the TGBA phase in free-standing films

A model of filament nucleation in the twist grain boundary A (TGBA) phase in free-standing smectic films is proposed. It is based on a concept of finite blocks of parallel smectic layers forming a helical structure in the interior of a film. In our model, the blocks resemble twin-like domains in smectic-A liquid crystal. The blocks are mediated to surrounding smectic layers in film either continuously (coherent twin boundary) or discontinuously via dislocation loops wrapping up blocks. Edge components of dislocation loops form incoherent twin boundary. Screw components forming twist grain boundary connect neighbour blocks among themselves. Nucleation of TGBA filament in a film is treated using a simplified model based on isotropic smectic-A elastic theory. Discussion showed that filaments can be nucleated just below the transition temperature from the isotropic to the TGBA phase under slow temperature decrease. The nucleation of dislocation loops is possible due to low compression modulus of material which can be expected just below the transition temperature.     

Surface tension of some liquid crystals in the cyanobiphenyl series

The temperature dependence of the surface tension was measured by the pendant drop method for four compounds from the homologous series of alkylcyanobiphenyls (nCB), in the nematic liquid crystal and isotropic phases. For 8CB (octylcyanobiphenyl) the temperature dependence was also measured in the smectic range. Not very close to the isotropic transition temperature, and with the exception of 8CB, the surface tension decreases with increase in temperature in the nematic range. A downward jump at the transition temperature was observed for all liquid crystals studied. The shape of the drop in the smectic A phase of 8CB gives indications of stratification in a system of terraces.     

Calorimetric study of phase transitions in a liquid-crystal-based microemulsion

A lyotropic inverse micelle phase composed of water, thermotropic liquid-crystal octylcyanobiphenyl (8CB), and surfactant (DDAB) was studied by using high-resolution calorimetry on several mixtures with 3%, 8%, and 15% micelle concentration. Calorimetric results show strong depression of the isotropic to nematic (I-N) phase-transition temperature. Broad heat-capacity anomalies show the existence of a wide coexistence range of isotropic, nematic, and smectic-A phases, which mimics the behavior of a new nearly stable thermodynamic phase. An observation of the rather sharp almost bulklike nematic to smectic-A (N-A) transition at low-temperatures indicates that our heat capacity results are consistent with the phase separation scenario in which significant number of micelles is expelled during I-N conversion leaving almost pure nematic phase at lower temperatures. It was found that micelles get almost completely remixed on heating the mixture back to the isotropic phase.     

Glassiness of thermotropic liquid crystals across the isotropic-nematic transition

The orientational dynamics of thermotropic liquid crystals across the isotropic-nematic phase transition have traditionally been investigated at long times or low frequencies using frequency domain measurements. The situation has now changed significantly with the recent report of a series of interesting transient optical Kerr effect (OKE) experiments that probed orientational relaxation of a number of calamitic liquid crystals (which consist of rod-like molecules) directly in the time domain, over a wide time window ranging from subpicoseconds to tens of microseconds. The most intriguing revelation is that the decay of the OKE signal at short to intermediate times (from a few tens of picoseconds to several hundred nanoseconds) follows multiple temporal power laws. Another remarkable feature that has emerged from these OKE measurements is the similarity in the orientational relaxation behavior between the isotropic phase of calamitic liquid crystals near the isotropic-nematic transition and supercooled molecular liquids, notwithstanding their largely different macroscopic states. In this article, we present an overview of the understanding that has emerged from recent computational and theoretical studies of calamitic liquid crystals across the isotropic-nematic transition. Topics discussed include (a) single-particle as well as collective orientational dynamics at a short-to-intermediate time window, (b) heterogeneous dynamics in orientational degrees of freedom diagnosed by a non-Gaussian parameter, (c) fragility, and (d) temperature-dependent exploration of underlying energy landscapes as calamitic liquid crystals settle into increasingly ordered mesophases upon cooling from the high-temperature isotropic phase. A comparison of our results with those of supercooled molecular liquids reveals an array of analogous features in these two important classes of soft matter systems. We further find that the onset of growth of the orientational order in the parent nematic phase induces translational order, resulting in smectic-like layers in the potential energy minima of calamitic systems if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. We discuss implications of this startling observation. We also discuss recent results on the orientational dynamics of discotic liquid crystals that are found to be rather similar to those of calamitic liquid crystals.     

Small angle X-ray scattering study of chiral side chain liquid crystalline polymers in 5CB and 8CB solvents

Small angle X-ray scattering was used to examine the new chiral side chain liquid crystalline polyacrylates (P_4M and P_11M) and their mixtures (2 wt %) in the low molar mass nematogenics 4'-n-pentyl-4-cyanobiphenyl (5CB) and 4'-octyl-4-cyanobiphenyl (8CB). Complementary data were obtained by polarizing optical microscopy. In agreement with previous studies, the mesophases of the bulk polymers show a dependence on the aliphatic spacers linking the mesogenic units to the polymer backbone. Chiral nematic and smectic A₁ phases were observed for the polyacrylates with four (P_4M) and eleven (P_11M) methylene units as spacers, respectively. In solution with 5CB and 8CB, P_4M exhibits an injected smectic phase, whereas P_11M maintains the smectic arrangement already observed in the bulk, with swollen smectic layers. In all the mixtures, layer stability was found to depend on the liquid crystal used as solvent, as well as on the temperature. At temperatures corresponding to the nematic 5CB and 8CB, the coexistence of two mesophases was observed in the mixtures. Moreover, with the liquid crystal solvents in the isotropic phase, microstructures suspended in the solvent matrix containing the liquid crystalline polymer in the smectic arrangement were detected.     

Existence of time lag in crystalline to smectic A (K–SmA) phase transition of 4-decyl-4-biphenylcarbonitrile (10CB) liquid crystal

This study explores the presence of time lag in crystalline to smectic A (K–SmA) phase transition of 4-decyl-4-biphenylcarbonitrile (10CB) liquid crystal. A non-isothermal heating and cooling study were performed for 10CB liquid crystal using calorimetric technique where heating scan was performed from 250 to 350 K, and cooling scan was performed from 350 to 250 K. A clear difference in K–SmA phase transition was observed between heating and cooling scans. An attracting inclination effect in K–SmA transition was observed on cooling which is completely absent on heating. The inclination of the K–SmA transition peak increases and shows an existence of time lag during cooling, whereas other family member shows no effect i.e., 8CB. K–SmA peak shows a lower enthalpy with higher activation when compared with 8CB. The presence of time lag and increase in activation can be explained in terms of the density and nature of the material.     

Surface tension of some liquid crystals in the cyanobiphenyl series

The temperature dependence of the surface tension was measured by the pendant drop method for four compounds from the homologous series of alkylcyanobiphenyls (nCB), in the nematic liquid crystal and isotropic phases. For 8CB (octylcyanobiphenyl) the temperature dependence was also measured in the smectic range. Not very close to the isotropic transition temperature, and with the exception of 8CB, the surface tension decreases with increase in temperature in the nematic range. A downward jump at the transition temperature was observed for all liquid crystals studied. The shape of the drop in the smectic A phase of 8CB gives indications of stratification in a system of terraces.     

Synthesis and properties of organic–inorganic hybrid liquid crystal gels

Organic–inorganic hybrid liquid crystal (LC) gels have been synthesised by the thiol-ene reaction of a multifunctional cyclic siloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (TVMCTS) and alkane dithiols, 1,6-hexanedithiol (HDT) or 1,9-decanedithiol (DDT), in LC matrices, 4-cyano-4?-pentylbiphenyl (5CB) or 4′-n-octyl-4-cyano-biphenyl (8CB). The LC gels were prepared in an isotropic phase at 70°C or mesophases at 25°C using radical initiators. The phase transition temperatures from a mesophase to an isotropic phase of the resulting gels were lower than those of the original LCs. The gels containing 8CB (8CB gels) prepared at 25°C showed two phase transitions: smectic-to-nematic and nematic-to-isotropic transitions. By contrast, the 8CB gels synthesised in the isotropic phase showed only one phase transition from smectic phase directly to isotropic phase. Reaction conversions in the LC gels prepared at 70°C were higher than that in the gels prepared at 25°C. Scanning microscopic light scattering analysis of the LC gels cleared homogeneous small size mesh with a small amount of large defect. Polarisation micrographs of the LC gels showed framed optical textures derived from the LC molecules at room temperature. The LC gels containing more than 90 wt% of LC showed electro-optic response.     

Crystal-liquid crystal binary phase diagrams

We propose a new theoretical scheme for the binary phase diagrams of crystal-liquid crystal mixtures by a combination of a phase field model of solidification, the Flory-Huggins theory for liquid-liquid mixing and Maier-Saupe-McMillan (FH-MSM) model for nematic and smectic liquid crystal orderings. The phase field theory describes the crystal phase transition of anisotropic organic crystal and/or side chain liquid crystalline polymer crystals while the FH-MSM model explains isotropic, nematic and smectic-A phase transitions. Self-consistent calculations reveal several possible phase diagram topologies of the binary crystal-liquid crystal mixtures. The calculated phase diagrams were found to accord well to the reported experimental results.     

Experimental assessment of quasi-binary picture of thermotropics: induced smectic A phase in 7CB-n-heptane system

Quasi-binary (QB) picture of thermotropics, which regards a neat thermotropic liquid crystal as a binary system consisting of (semi)rigid core and molten alkyl chain, was assessed experimentally for the most famous (and representative) thermotropic mesogenic series nCB. By adding n-heptane as solvent, the smectic A phase was induced in 7CB-n-heptane system. Small angle x-ray diffraction showed that the QB picture holds not only in the phase behavior but also in the structure. It is suggested that the melting of 8CB and 9CB to isotropic liquid via smectic and nematic liquid crystals can be understood as a thermotropic-lyotropic crossover.     

Mesophase study of pure and doped cyanobiphenyl liquid crystals with salen-type systems

Two salen Schiff base ligands derived from the condensation of ethylendiamine on salicylaldehyde and 5-chlorosalicylaldehyde, namely N,N′-bis(salicylidene)ethylene-diamine (L1) and N,N′-bis(5-chlorosalicylidene)ethylene-diamine (L2) as well as two of their iron(III) and nickel(II) complexes, were prepared and then used as doping agents of two thermotropic liquid crystals (LCs) of cyanobiphenyl type, namely 4-cyano-4′-n-pentyl-biphenyl (5CB) and 4-cyano-4′-n-octyl-biphenyl (8CB). The study of the mesophase of pure and doped LCs was carried out by UV–visible spectroscopy equipped with a heating compartment for precise temperature control, differential scanning calorimetry and polarised optical microscopy. The characteristic nematic/isotropic and smectic-A/nematic transition temperatures of 5CB- and 8CB-based systems were measured and then compared to those of the literature concerning pure 5CB and 8CB. Optical microscopy results revealed the existence of Schlieren and focal conic textures of the nematic and smectic states, respectively, both of pure and doped LCs. The homogeneity of the obtained guest–host systems was proven by the linear evolution of their transition temperatures as function of the solute concentration, with correlation factors close to unity.     

端基含36个4-硝基偶氮苯介晶基元的二代树状碳硅烷的液晶性研究

液晶树状物的液晶相态分别为SA相、SC相、SC^*相、向列相、胆甾相、盘状相、立方相和群聚向列相,而SE相液晶树状物尚未见报道,本文报道含吸电性端基(硝基)偶氮苯介晶基元二代树状物(D2)的液晶行为。     

The stabilization of smectic A phases in mixtures of twinned-calamitic, metal organic complexes with 2,4,7-trinitro-9-fluorenone

The liquid crystal properties of binary mixtures of copper- and palladium-containing, twinnedcalamitic, metal organic complexes with the electron acceptor 2,4,7-trinitro-9-fluorenone (TNF) are reported. The smectic A to isotropic transition temperature of the pure metal organic component is increased on mixing. Furthermore, only smectic A behaviour is exhibited by the mixtures compared with smectic A and C phases for the pure metal organic complexes. The stabilization of the smectic A phase in these mixtures is found to be due to a weak charge transfer type interaction.     

Anomalous behaviours of the heat capacity in a liquid crystal showing a re-entrant isotropic phase

High resolution a.c. calorimetric measurements have been carried out on a liquid crystal 2-{4-[(R)-2-fluorohexyloxy]phenyl}-5-{4-[(S)-2-fluoro-2-methyldecanoyloxy]phenyl}pyrimidine (RSFPPY), determined the present measurement revealed precise temperature dependence of the heat capacity over a wide temperature range including the phase transition temperatures. The isotropic-chiral smectic C transition was anomalous in that it showed quite different behaviours depending on whether the measurement was made on heating or cooling; that is attributed to the relaxational character of the transition. A new non-transitional feature in the isotropic phase was found, corresponding to a very broad heat capacity peak over a 30 K temperature range. This indicates an existence of a new phase, possibly some kind of blue phase, at the lower temperature side of the isotropic phase. (RSFPPY), determined the present measurement revealed precise temperature dependence of     

Small angle X-ray scattering study of chiral side chain liquid crystalline polymers in 5CB and 8CB solvents

Small angle X-ray scattering was used to examine the new chiral side chain liquid crystalline polyacrylates (P_4M and P_11M) and their mixtures (2?wt?%) in the low molar mass nematogenics 4′-n-pentyl-4-cyanobiphenyl (5CB) and 4′-octyl-4-cyanobiphenyl (8CB). Complementary data were obtained by polarizing optical microscopy. In agreement with previous studies, the mesophases of the bulk polymers show a dependence on the aliphatic spacers linking the mesogenic units to the polymer backbone. Chiral nematic and smectic A₁ phases were observed for the polyacrylates with four (P_4M) and eleven (P_11M) methylene units as spacers, respectively. In solution with 5CB and 8CB, P_4M exhibits an injected smectic phase, whereas P_11M maintains the smectic arrangement already observed in the bulk, with swollen smectic layers. In all the mixtures, layer stability was found to depend on the liquid crystal used as solvent, as well as on the temperature. At temperatures corresponding to the nematic 5CB and 8CB, the coexistence of two mesophases was observed in the mixtures. Moreover, with the liquid crystal solvents in the isotropic phase, microstructures suspended in the solvent matrix containing the liquid crystalline polymer in the smectic arrangement were detected.     

Landau theory for isotropic,nematic, smectic-A,and smectic-C phases

ABSTRACT

We use the Landau theory of phase transitions to describe the phase diagram of a liquid crystal displaying the isotropic (i), nematic (N), smectic-A and smectic-C phases. The order parameter of the smectic-C phase is defined as the projection of the director on the plane of the smectic layers, vanishing in the smectic-A phase. We present a detailed phase diagram that shows transition between any two of these phases, containing a triple point INA, a Lifshitz point NAC, a tricritical at the NA line, and a critical end point IAC. As one approaches the NC line from the smectic-C phase, the tilt angle approaches a nonzero value, but if the AC line is approached, the tilt angle vanishes according to the distance to the AC line to the power 1/2.     

The effect of magnetic nanoparticles upon the smectic-A to smectic-C* phase transition

We report on wide-angle X-ray scattering measurements along the smectic-A to chiral ferroelectric smectic-C* phase transition of the liquid crystal SCE9 and its mixture with maghemite magnetic nanoparticles of typical dimension 20 nm. The temperature profiles of the tilt angle are fitted by an extended mean-field model. Neither pre-transitional order effects nor variations in the SmA layer thickness are observed, indicating a rather negligible influence of these nanoparticles upon the molecular orientation at the smectic-A to smectic-C* phase transition of SCE9. These results are very different from what was observed for smaller CdSe nanoparticles (3.5 nm) where both a dilation of the smectic layers in the SmA phase and a crossover behaviour for the smectic-A to smectic-C* transition away from tricriticality have been observed for analogous concentrations.     

Reentrant phenomena in cyano substituted biphenyl esters containing flexible spacers

A number of 4'-substituted phenyl 4-(4'-cyano-4-oxybiphenyl)butanoates have been synthesized to study the effects of the -O-(CH₂)₃COO- inter-ring linkage on mesomorphic behaviour. Transition temperatures have been determined and are compared with those of the phenyl cyanobiphenylmethanoate analogues. In general, the butanoates exhibit lower melting points but in all cases, a lower nematic-isotropic transition is observed. An interesting feature of some members of the butanoate series is the presence of several reentrant mesophases. A unique phenomenon observed while studying the behaviour of one of the butanoates was the appearance of smectic filaments from the isotropic liquid on cooling. These filaments, through an unusual process, eventually form the typical smectic A texture. Formation of an S_A phase from the isotropic liquid or the nematic phase in this fashion has not been reported previously.