Physical properties of mixtures of low molar mass nematic liquid crystals with photochromic fulgide guest dyes

Abstract

This paper considers how a low concentration (> 2 per cent w/w) of a photochrome dissolved in a liquid crystal affects the physical properties of the host mesogen. A novel class of photochromes, the fulgide based dyes, have been used to give a new approach in this area of study. Unlike many other light active dyes, the fulgides exhibit only a relatively small shape change. Because of this, the influence of the changes in the physical properties of the guest (for example, the dipole moment) are readily studied. Both thiophene and furan fulgide doped liquid crystal systems were studied in the irradiated and non-irradiated states and as a function of concentration. The changes in phase transition temperature, refractive index and order parameter for these various states as compared to the pure host liquid crystal have been measured to investigate the way in which the dye alters the mesomorphic properties of the host, on a molecular level.     

Electroclinic behaviour of polymer doped low molar mass ferroelectric liquid crystals

Abstract

Recently there has been much interest in the electroclinic effect due to its potential application in high speed optical modulators and grey scale displays. In present materials, however, the electroclinic effect is very dependent on temperature and falls off rapidly with increasing temperature. This limits the useful device operating range. In this paper the electroclinic behaviour of new, side chain polymer doped, low molar mass ferroelectic liquid crystal mixtures is reported. By measuring the rate of change of the electroclinic coefficient with temperature it is shown that the temperature range over which the electroclinic effect exists increases with polymer concentration. Data are also presented on electroclinic response times.     

Electroclinic behaviour of polymer doped low molar mass ferroelectric liquid crystals

Recently there has been much interest in the electroclinic effect due to its potential application in high speed optical modulators and grey scale displays. In present materials, however, the electroclinic effect is very dependent on temperature and falls off rapidly with increasing temperature. This limits the useful device operating range. In this paper the electroclinic behaviour of new, side chain polymer doped, low molar mass ferroelectic liquid crystal mixtures is reported. By measuring the rate of change of the electroclinic coefficient with temperature it is shown that the temperature range over which the electroclinic effect exists increases with polymer concentration. Data are also presented on electroclinic response times.     

Ferroelectric and antiferroelectric low molar mass organosiloxane liquid crystals

The present paper is a study of the ferroelectric and antiferroelectric behaviour in low molar mass organosiloxane liquid crystal materials classed as mono-mesogens (AB type) and bi-mesogens (ABA type). A systematic study of series of materials all based on the same chiral mesogenic moiety is presented. The mesogen is a biphenylyl benzoate with a halogen X attached laterally to the benzoate ring which is closest to the chiral centre. Three homologous series, where the halogen is either fluorine, chlorine or bromine, are investigated. The number of silicon atoms in the linkage or end group is varied between two and nine. It is found that the materials have a broad (40 C) ferroelectric or antiferroelectric phase with a high P s (90nC cm2). The siloxane moiety forces the tilt angle to a temperature independent value close to 45. The antiferroelectric order is observed only in bi-mesogens with an odd number of silicon atoms in the siloxane link. The antiferroelectric order is attributed to the conformation of the molecule rather than to antiferroelectric interactions between layers.     

Synthesis and thermal transitions of a soluble,main chain,nematic liquid crystalline polymer exhibiting a kinetically trapped,disordered structure

An aromatic copolyester composed of 25 mol % phenyl hydroquinone, 10 mol % isophthalic acid, 40 mol % chloroterephthalic acid, and 25 mol % t-butyl hydroquinone (PICT) has been synthesized. This amorphous, glassy polymer is soluble in common organic solvents such as methylene chloride. Thin, solution-cast films may be prepared which are in a metastable, vitrified, optically isotropic state. On first heating of an isotropic film at 20°C/min in a calorimeter, one glass transition is observed at low temperature (approximately 49°C) and is ascribed to the glass/rubber transition of the metastable, isotropic polymer. This thermal event is followed by a small exotherm due to the development of order during the scan, which results in a second T_g at approximately 125°C. This T_g is associated with the glass/rubber transition of the ordered polymer. Nematic order can be developed by thermal annealing. The lower T_g increases toward the upper T_g as annealing time is increased. For an initially isotropic film annealed at 90°C, the increase of the lower T_g with annealing time and the increase in birefringence observed by optical microscopy are governed by similar kinetics. Isotropization occurs in the temperature range of 250–300°C. The nematic polymer is slightly more dense than its isotropic analog. No detectable differences between isotropic and nematic samples were observed in rotating frame proton spin lattice relaxation times. © 1996 John Wiley & Sons, Inc.     

Antiferroelectric and ferrielectric liquid crystalline low molar mass materials and polymers

Novel liquid crystalline Low Molecular Mass (LMM) materials bearing two chiral lactate groups, as well as compounds of like structure to MHPOBC have been synthesized. All the LMM compounds exhibit the SmC*A (antiferroelectric) and/or SmC*gamma (ferrielectric) phases. The mesogens have been incorporated as pendant groups on polymer backbones of three different natures to prepare side chain liquid crystalline copolysiloxanes, homopolysiloxanes and homopolyacrylates. The investigation of the polymers by means of miscibility studies showed that the antiferro- and ferri-electric phases are strongly destabilized in the coposiloxanes and homopolysiloxanes, while in the homopolyacrylates a large temperature range mesophase is found to be miscible with the SmC*A phase. The physical properties of the mesophases and their stability, both for the LMM materials and the polymers, are presented and discussed.     

Novel liquid crystalline structures of a chiral side chain polymer and its phase transitions

Two novel smectic bilayer structures have been identified in an enantiomerically enriched chiral side chain polymer containing the highly dipolar nitrile group at stereocentres. The structures were characterized by electron diffraction, electron microscopy, and X-ray diffraction. In both phases each smectic layer has a bilayer structure with backbones and spacers confined in a thin disordered region between two sublayers of mesogenic segments. One of the structures which we denote as CrE* has the unusual feature of having its side chains arranged parallel to the layer normal in spite of its enantiomeric bias and twisted nature. In the second structure side chains are tilted by 34.8° with respect to the layer normal and we denote this phase as CrH*_c In both structures each sublayer contains three different orientations of orthorhombic (CrE) or monoclinic (CrH*_c) lattices which are related to one another by rotations of ± 60° about the c-axis. In both the CrH*_c and the CrE* phases, lattices in each sublayer are regularly rotated about the c-axis by 5.9° relative to those in the adjacent sublayer. The observation of a chiral CrH phase is uncommon and in this specific case the structure is unique since the rotation between adjacent layers occurs about the sidechain axis (c-axis) (CrH*_c) and not about the layer normal (c-axis) (CrH*_c). We believe the system undergoes a change in molecular organization from CrH*_c to CrE* as a result of a chemical reaction which joins a fraction of the stereocentres through covalent bonds. With increasing temperature the CrE* structure was found to transform to a special orthorhombic untwisted smectic phase in which a = 31/2b, denoted here as CrE_h. The structure then transforms to a hexatic S_B phase and finally to a S_A phase at yet higher temperatures.     

Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4-n -hexyloxy-4′-cyanobiphenyl (6OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0–29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.     

Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4- n -hexyloxy-4'-cyanobiphenyl (6OCB) and 4- n -octyloxy-4'-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0-29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.     

Structure and phase transitions of a liquid crystalline polymer

Summary The structures, textures as well as thermodynamic properties of a side chain polymer exhibiting a liquid crystalline phase in addition to a partially crystalline state and the isotropic fluid state were investigated. Furthermore the kinetics of phase transitions between these states were analyzed. It was found that the properties of this polymer are intermediate between that of low molecular weight liquid crystals and common polymers. In particular it was observed that the relation between the liquid crystalline texture and the structure is different from that of low molecular weight liquid crystals and that the properties of the crystalline and liquid crystalline state depend strongly on the tacticity of the polymer.

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Zusammenfassung Für ein Seitenkettenpolymeres, das zusätzlich zum teilkristallinen Zustand und zur isotropen Schmelze einen flüssig-kristallinen Zustand aufweist, wurden die Strukturen und Texturen untersucht sowie thermodynamische Eigenschaften. Außerdem wurde die Kinetik der Phasenumwandlungen analysiert. Es zeigt sich, daß die Eigenschaften zwischen denen üblicher Polymerer und denen von niedrigmolekularen flüssigen Kristallen liegen. Insbesondere zeigte sich, daß die Beziehung zwischen molekularer Struktur und Textur von der bei niedrigmolekularen flüssigen Kristallen abweicht, und daß die Taktizität der Kette einen starken Einfluß auf die Eigenschaften nicht nur der kristallinen Phase sondern auch der flüssig-kristallinen Phase ausübt.

     

Chiral nematic phase in hydrogen-bonded blends of a side-chain smectic polymer with low molar mass dopants

The possibility of chiral nematic mesophase induction in blends of a smectic A side-chain liquid-crystalline copolymer with low molar mass dopants was studied. The chirality of the initial copolymer was determined by the cholesterol optical active groups; however, in the individual state it was not able to form any chiral liquid-crystalline phases. We have shown that the induction of the chiral nematic phase becomes possible in blends of such a copolymer with low molar mass dopants that are stabilized by hydrogen bonding. Phase behavior and optical properties of the blends were studied with X-ray scattering, differential scanning calorimetry and polarizing microscopy. Owing to hydrogen bonding the blends are stable over a wide range of contents and temperatures. The nature of the end group in the dopant molecules is shown to have an important influence on the chiral mesophase induction concentration and the clearing temperatures of the blends. Temperature and concentration dependences of the selective reflection maximum wavelength in the chiral nematic phase were also studied.

A statistical model for transitions in nematic liquid crystals

The two-lattice model of Lennard-Jones and Devonshire has been modified and applied to the study of the transition from the nematic to the isotropic phase. We have used the concept of external degrees of freedom for molecules introduced by Prigogine and applied to the case of chain liquids.     

Direct decoration of disclinations by solidification-induced band texture for a nematic side chain liquid crystalline polymer

For a nematic polymethacrylate side chain liquid crystalline polymer, g 154 N 298 I (°C), the solidification-induced band texture has been observed aligned along the disclination under a polarizing optical microscope, when the specimen was quenched from 280°C to room temperature. The decoration technique of solidification-induced band texture, which is usually reported for main chain liquid crystalline polymers, was then introduced to reveal the director field pattern along a disclination for this side chain liquid crystalline polymer. It was found by infra-red dichroism measurements that the director orientation is parallel with the direction of the band. On this basis, disclinations with strength s=±1/2 and s=±1 were mapped according to the corresponding pattern of solidification-induced band texture. In addition, two types of inversion wall, loop-like and splay-type walls, were also found to be decorated by the solidification-induced band texture.     

Aromatic liquid crystals with a trifluoromethyl group in the terminal chain for use in nematic LC mixtures

A new class of compounds suitable for LCD applications has have synthesized, incorporating a trifluoromethyl group in the terminal alkoxy or alkenyloxy chain. These compounds fulfil many of the specifications for use in TN-LCDs. Compounds containing several aromatic rings were synthesized with a view to producing compounds of high birefringence. This aspect also included the synthesis of compounds containing a carbon-carbon triple bond. Materials with three phenyl rings were also prepared in an attempt to produce nematic liquid crystals with a high clearing point and a high birefringence. Molecules containing a lateral fluoro substituent were synthesized in order to generate a high positive value of the dielectric anisotropy, a low melting point and no smectic mesophases. A series of compounds incorporating a carbon-carbon double bond was prepared in an attempt to produce compounds with a high nematic clearing point and a high birefringence.     

Collective and molecular dynamics in low molar mass and polymeric ferroelectric liquid crystals

By use of a novel sample preparation technique, it is possible to measure with one sample cell the collective and molecular dynamics (10^-1 Hz-10⁹ Hz) of macroscopically (in bookshelf geometry) oriented ferroelectric liquid crystals. Below 10⁶ Hz, two ferroelectric modes, Goldstone- and soft-mode, are observed, being assigned to fluctuations of the phase and amplitude of the helical superstructure respectively. Between 10⁶ and 10⁹ Hz, one dielectric loss process exists, the β-relaxation which originates from the librational motion (hindered rotation) of the mesogen around its molecular long axis. This process does not split or broaden at the non-ferroelectric-ferroelectric phase transition and it has an Arrhenius type temperature dependence. In comparing a racemic mixture with a chiral sample, it performs a similar frequency and temperature dependence. The experimental findings for the β-relaxation are in qualitative contrast to the predictions of the (generalized) Landau expansion of the free energy at the non-ferroelectric-ferroelectric phase transition. The experiment also leads to a modified understanding for the molecular origin of ferroelectricity in FLCs.     

Aromatic liquid crystals with a trifluoromethyl group in the terminal chain for use in nematic LC mixtures

A new class of compounds suitable for LCD applications has have synthesized, incorporating a trifluoromethyl group in the terminal alkoxy or alkenyloxy chain. These compounds fulfil many of the specifications for use in TN-LCDs. Compounds containing several aromatic rings were synthesized with a view to producing compounds of high birefringence. This aspect also included the synthesis of compounds containing a carbon-carbon triple bond. Materials with three phenyl rings were also prepared in an attempt to produce nematic liquid crystals with a high clearing point and a high birefringence. Molecules containing a lateral fluoro substituent were synthesized in order to generate a high positive value of the dielectric anisotropy, a low melting point and no smectic mesophases. A series of compounds incorporating a carbon-carbon double bond was prepared in an attempt to produce compounds with a high nematic clearing point and a high birefringence.     

Numerical analysis for a nematic droplet in polymer dispersed liquid crystals

Starting from the Landau-de Gennes free energy expression, the author has numerically analysed the director pattern in a nematic droplet of polymer dispersed liquid crystals. The nematic director has been understood as the eigenvector, which corresponds to the largest eigenvalue of the tensor order parameter. To investigate the droplet structure influence, all equations have been treated on the curvilinear coordinate system which is generated along the droplet boundary. In the case of spherical and spheroidal droplets with normal strong anchoring, the director exhibits an axial configuration and a disclination ring. The ring radius and the capactiance of the system change without hysteresis with the applied voltage.     

Internal orientations in externally deformed nematic polymer liquid crystals

The system of linear polymer liquid crystal (PLC) macromolecules, each modeled by semiflexible chain of alternate connected flexible and stiff rodlike sequences, is externally deformed. As a result, two orientation phases for hard rods are generated. One of them is nematic N+ with orientation parameter s>0; this has the place in monomer liquid crystal (MLC) systems and in PLCs. The nematic N- phase with s>0 appears in deformed PLCs only. This causes the fact that orientation of PLC chains, as a whole, is generated also by the system deformation. A discussion of that effect is the main goal of this article. The change of orientation is also discussed dependent on changes of the system temperature and parameters of the chain structure, such as the liquid crystal component concentration, contour lengths of stiff and flexible parts, and internal interactions parameters. Average shape of PLC chain and the shape anisotropy are calculated and discussed.