Simultaneous determination of fundamental parameters for ferroelectric liquid crystals

An analysis of an experimental technique which allows for a simultaneous determination of several parameters with special interest for ferroelectric liquid crystals is presented. These parameters are the spontaneous polarization, the rotational viscosity and the switching time. In addition, the susceptibility associated with the soft mode free of contributions related to the helicoidal structure can also be obtained. The experimental results for these parameters for the ferroelectric liquid crystal HDOBACEEC are reported. A comparison between the switching time values deduced from the rotational viscosity and those obtained by optical measurements is performed.     

Measurement of the rotational viscosity of ferroelectric liquid crystals based on a simple dynamical model

Rotational viscosity and spontaneous polarization are the most important properties of a ferroelectric liquid crystal with regard to its switching time in surface stabilized or a.c. field stabilized displays. Whereas there is an abundant literature about spontaneous polarization, only a few attempts have been made to determine the rotational viscosity. We set up a model for the electric response of a ferroelectric liquid crystal cell on application of an electric field. For the application of a triangular wave voltage we derive a relation between the rotational viscosity, the spontaneous polarization, the tilt angle, the maximum induced polarization current and the electric field strength. Experiments are carried out on several ferroelectric liquid crystals and the derived relation was used to determine the rotational viscosity. The relation between the rotational viscosity and the polarization on the one hand and the optical switching time on the other hand is discussed in some detail.     

Viscosity coefficients of smectics C*

By extending the statistical theory of rheological properties of nematics, we derive elementary expressions for all phenomenological viscosity coefficients of ferroelectric smectics C* in terms of a small number of parameters. The results permit estimates of signs and ratios of viscosity coefficients and their tilt angle dependence. It is shown that a number of coefficients generally appear to be very small and can be neglected in practical calculations. We discuss also the influence of molecular biaxiality on the rotational viscosity of smectics C.     

Effect of fluorination on the phase sequence,dielectric and electro-optical properties of ferroelectric and antiferroelectric mixtures

Four multicomponent room temperature mixtures were formulated using a pyrimidine-based achiral matrix as host and four terphenyl-based ester chiral compounds as dopants. Among the four mixtures, two exhibit antiferroelectric and two other exhibit ferroelectric phases at room temperature. Dopant molecules differ from each other by position and number of fluorine atom substitution at the benzoate group of the molecular rigid core. Number and location of fluorine atoms in the dopant structure show significant effect on the phase sequences as well as on different physical properties. All the mixtures found to have moderate spontaneous polarisation, high tilt angle, very fast switching time and low viscosity which are important for liquid crystal-based display applications.     

Ferroelectric properties of mixtures of a liquid crystalline polymer and its side-group mesogen

We present the results of our studies of the ferroelectric properties of mixtures of a high polarization, ferroelectric liquid crystalline copolymer and its side-group antecedent, a high polarization, low molecular weight, ferroelectric mesogen. These two materials are found to be completely miscible in all proportions. Spontaneous polarization values and electro-optical response times are found to be monotonic functions of the weight percentage of the mesogen in the mixture, while optical tilt angles do not exhibit such a monotonic dependence.     

Dielectric, viscosity, and pitch measurements of a ferroelectric liquid crystal exhibiting the phase sequence smectic M-smectic C

A chiral liquid crystal compound exhibiting the ferroelectric smectic C phase and the recently discovered ferroelectric smectic M phase has been studied by measurements of the Goldstone-mode relaxation frequency and dielectric strength, the spontaneous polarization, the tilt angle and the helical pitch. The data allow the determination of the Goldstone-mode rotational viscosity and the pitch controlling elastic constant. The results indicate that the smectic M phase is characterized by a larger molecular order within the smectic layers compared to the smectic C phase confirming the assumption of a tilted hexatic structure for the smectic M phase.     

Ferroelectric properties of mixtures of a liquid crystalline polymer and its side-group mesogen

Abstract

We present the results of our studies of the ferroelectric properties of mixtures of a high polarization, ferroelectric liquid crystalline copolymer and its side-group antecedent, a high polarization, low molecular weight, ferroelectric mesogen. These two materials are found to be completely miscible in all proportions. Spontaneous polarization values and electro-optical response times are found to be monotonic functions of the weight percentage of the mesogen in the mixture, while optical tilt angles do not exhibit such a monotonic dependence.     

Fluorescent dye guest-host effects in advanced ferroelectric liquid crystals

Previous work has shown that guest-host ferroelectric systems incorporating dichroically absorbing dyes are suitable for use in colour display applications. These utilize either the dichroic absorption of a conventional dye, or the emission of a fluorescent dye. We present here the electrooptical properties of several advanced ferroelectric liquid crystals doped with a new fluorescent dye, coloured blue in emission. The data consists of measurements of tilt angle, response time, spontaneous polarization, and rotational viscosity, from which we conclude that certain hosts are not adversely affected by the fluorescent dopants. These results are then discussed in connection with the use of these mixtures in two novel colour display configurations, which are also presented, utilizing either the dichroic absorption or the polarized fluorescence of the fluorophore guests.     

Rotational viscosity of ferroelectric liquid-crystalline polysiloxanes

Some physical parameters of comb-shaped ferroelectric liquid-crystalline polymers were measured. Their rotational viscosities are two or three orders of magnitude larger than that of low molecular weight ferroelectric liquid crystals. Furthermore, they are found generally to be proportional to the second power of the weight-average molecular weight. Spontaneous polarization of the ferroelectric liquid-crystalline polymers has little dependence on molecular weight.     

Fluorescent dye guest-host effects in advanced ferroelectric liquid crystals

Abstract

Previous work has shown that guest-host ferroelectric systems incorporating dichroically absorbing dyes are suitable for use in colour display applications. These utilize either the dichroic absorption of a conventional dye, or the emission of a fluorescent dye. We present here the electrooptical properties of several advanced ferroelectric liquid crystals doped with a new fluorescent dye, coloured blue in emission. The data consists of measurements of tilt angle, response time, spontaneous polarization, and rotational viscosity, from which we conclude that certain hosts are not adversely affected by the fluorescent dopants. These results are then discussed in connection with the use of these mixtures in two novel colour display configurations, which are also presented, utilizing either the dichroic absorption or the polarized fluorescence of the fluorophore guests.     

Properties of new ferroelectric materials

A homologous series of chiral 4-(3-methylpentyl)benzenethio-4′-n-alkoxy-benzoates has been studied. These thioesters display a ferroelectric, chiral smectic C phase in addition to cholesteric and smectic A phases. A comparison is made between the thioester series and a phenylbenzoate, having the same molecular end group. The effect of the different central linkage on the transition temperature, and on the physical and ferroelectric liquid crystal (FLC) properties has been investigated. Several mixtures, containing these thioester components, were calculated and formulated to obtain room temperature chiral smectic C phases. Spontaneous polarization P_s values and electro-optical response times are correlated with chemical structures. Although these thioesters have very low P _s values, they are useful components for FLC mixtures because of their convenient chiral smectic C temperature ranges and their low viscosities.     

Rotational viscosity of ferroelectric liquid-crystalline polysiloxanes

Abstract

Some physical parameters of comb-shaped ferroelectric liquid-crystalline polymers were measured. Their rotational viscosities are two or three orders of magnitude larger than that of low molecular weight ferroelectric liquid crystals. Furthermore, they are found generally to be proportional to the second power of the weight-average molecular weight. Spontaneous polarization of the ferroelectric liquid-crystalline polymers has little dependence on molecular weight.     

Transport properties of CO2-expanded acetonitrile from molecular dynamics simulations

Carbon-dioxide-expanded liquids, which are mixtures of organic liquids and compressed CO2, are novel media used in chemical processing. The authors present a molecular simulation study of the transport properties of liquid mixtures formed by acetonitrile and carbon dioxide, in which the CO2 mole fraction is adjusted by changing the pressure, at a constant temperature of 298 K. They report values of translational diffusion coefficients, rotational correlation times, and shear viscosities of the liquids as function of CO2 mole fraction. The simulation results are in good agreement with the available experimental data for the pure components and provide interesting insights into the largely unknown properties of the mixtures, which are being recognized as important novel materials in chemical operations. We find that the calculated quantities exhibit smooth variation with composition that may be represented by simple model equations. The translational and rotational diffusion rates increase with CO2 mole fraction for both the acetonitrile and carbon dioxide components. The shear viscosity decreases with increasing amount of CO2, varying smoothly between the values of pure acetonitrile and pure carbon dioxide. Our results show that adjusting the amount of CO2 in the mixture allows the variation of transport rates by a factor of 3-4 and liquid viscosity by a factor of 8. Thus, the physical properties of the mixture may be tailored to the desired range by changes in the operating conditions of temperature and pressure.     

Rotational viscosity of fluids composed of linear molecules: an equilibrium molecular dynamics study

In this paper, we investigate the rotational viscosity for a chlorine fluid and for a fluid composed of small linear molecules by using equilibrium molecular dynamics simulations. The rotational viscosity is calculated over a large range of state points. It is found that the rotational viscosity is almost independent of temperature in the range studied here but exhibits a power-law dependency on density. The rotational viscosity also shows a power-law relationship with the molecular length, and the ratio between the shear and rotational viscosities approaches 0.5 for the longest molecule studied here. By changing the number of atoms or united atomic units per molecule and by keeping the molecule length fixed, we show that fluids composed of molecules which have a rodlike shape have a lower rotational viscosity. We argue that this phenomenon is due to the reduction in intermolecular connectivity, which leads to larger fluctuations around the values possessed by the fluid on average. The conclusions here can be extended to fluids composed of uniaxial molecules of arbitrary length.     

Dielectric,viscosity, and pitch measurements of a ferroelectric liquid crystal exhibiting the phase sequence smectic M–smectic C

Abstract

A chiral liquid crystal compound exhibiting the ferroelectric smectic C phase and the recently discovered ferroelectric smectic M phase has been studied by measurements of the Goldstone-mode relaxation frequency and dielectric strength, the spontaneous polarization, the tilt angle and the helical pitch. The data allow the determination of the Goldstone-mode rotational viscosity and the pitch controlling elastic constant. The results indicate that the smectic M phase is characterized by a larger molecular order within the smectic layers compared to the smectic C phase confirming the assumption of a tilted hexatic structure for the smectic M phase.     

Flow-alignment and viscosity rules for single-phase binary mesomorphic mixtures

A macroscopic model for incompressible homogeneous (single phase) binary nematic mixtures, under isothermal conditions is given. The rheological model is a generalization of the standard Ericksen's nematorheological model for single component uniaxial rod-like nematic liquid crystals. Its special cases include single component orthorhombic biaxial nematics and single component uniaxial nematics. The theory is used to formulate rules for the rotational viscosity and the reactive parameter of nematic mixtures in the presence of weak flows. The predicted mixture rules for the reactive parameter and rotational viscosity are analysed as a function of concentration and rotational viscosity ratio for various monomeric and polymeric mixtures, and for rod-rod, disc-disc, and rod-disc nematic mixtures. The mixture rules are used to compute alignment phase diagrams and alignment transition (orientational instability) thresholds.     

Molecular rotational potentials in the SC* phase of binary ferroelectric liquid crystal mixtures

The spontaneous polarization and tilt angle have been measured as a function of temperature and concentration in the S_C* phase of four binary ferroelectric liquid crystal mixtures. The substances have been chosen in a way that different situations could be studied, for example mixtures of a chiral substance (P_s non-zero) with a non-chiral one (P_s = 0) and mixtures of chiral compounds with the same sign of P_s as well as with opposite signs. The results have been interpreted by means of a molecular rotational model and potentials associated with the tilt as well as with the chirality have been determined as a function of concentration.     

Electrospray ionization mass spectrometry of terrestrial humic substances and their size fractions

Electrospray ionization mass spectrometry (ESI-MS) was used to evaluate the average molecular mass of terrestrial humic substances, such as humic (HA) and fulvic (FA) acids from a soil, and humic acid from a lignite (NDL). Their ESI mass spectra, by direct infusion, gave average molecular masses comparable to those previously obtained for aquatic humic materials. The soil HA and FA were further separated in size-fractions by preparative high performance size exclusion chromatography (HPSEC) and analyzed with ESI-MS by both direct infusion and a further on-line analytical HPSEC. Unexpectedly, their average molecular mass was only slightly less than for the bulk sample and, despite different nominal molecular size, did not substantially vary among size-fractions. The values increased significantly (up to around 1200 Da) after on-line analytical HPSEC for the HA bulk sample, at both pH 8 and 4, and for the HA size-fractions when pH was reduced from 8 to 4. It was noticed that HA size-fractions at pH 8 were separated by on-line HPSEC in further peaks showing average masses which progressively increased with elution volume. Furthermore, when the HA and NDL bulk samples were sequentially ultracentrifuged at increasing rotational speed, their supernatants showed mass values which were larger than bulk samples and increased with rotational speed. These variations in mass values indicate that the electrospray ionization is dependent on the composition of the humic molecular mixtures and increases when their heterogeneity is progressively reduced. It is suggested that the dominance of hydrophobic compounds in humic supramolecular associations may inhibit the electrospray ionization of hydrophilic components. Our results show that ESI-MS is reasonably applicable to humic substances only after an extensive reduction of their chemical complexity.     

Coordination polymers. XV. Influence of diols on the reaction between unsaturated polyesters and Mg ions

An increase in viscosity of reaction mixtures of low molecular mass, COOH, and alcoholic OH-terminated polyesters with MgO is considerably reduced by the presence of diols in the system. This effect is analogous with that described for the presence of water. Joint presence of water and diol results in an additive effect. The mechanism of this effect can be interpreted by coordination chemistry. In this system both diol and water saturate the coordination sphere of Mg²⁺ ion (as ligands). Consequently, the coordination of donor groups of polyester (terminal OH and ester carbonyl groups) is suppressed by reducing the extent of linking the polyester molecules with coordination bonds; that is, the average molecular mass of the system. Moreover, coordination of low-molecular ligands modifies the final molecular structure that occurs in the system. In addition, some kinetic effects are revealed in the process because the system is diffusion-controlled by the ever-increasing viscosity. This effect is also favorable to the coordination of low molecular mass ligands. All of these factors lead to a reduction in the increase of viscosity in the present system.