Theory of main chain nematic polymers with spacers of varying degree of flexibility

Main chain liquid crystal polymers are modelled as either worms or jointed rods. In reality they are composed of mesogenic units (rods) linked by spacers with varying degrees of flexibility. We present a molecular model to describe non-homogeneous nematic polymers. The model takes account of molecular parameters, such as the lengths of the mesogenic group and the spacer units, and the interactions between them. The spacers are found to have an order differing from the mesogenic units. If the spacer is not very long and thus in effect is inflexible, one end of the spacer can retain to some extent the orientation of the other end, allowing orientational correlation between spacers mediated by the intermediate mesogenic unit. This is important in giving the chain a global rod-like behaviour as the nematic field becomes strong or the temperature low. The nematic order of the two components (mesogens and spacers), the nematic-isotropic transition as well as the latent entropy are examined. Furthermore, the anisotropic conformations of the polymers are investigated, which show either rod-like or random walk behaviour. Comparison of our results with experiment is found to be satisfactory.     

Oligomeric rod-disc nematic liquid crystals

Six new oligomeric nematic liquid crystals are reported consisting of a triphenylene-based core attached to which are six 4-cyanobiphenyl units via flexible alkyl spacers.     

Viscoelastic properties of dilute nematic mixtures containing cyclic and hyperbranched liquid crystal polymers dissolved in a nematic solvent

The twist and bend viscosities of dilute solutions of cyclic and hyperbranched liquid crystal polymers (LCP) dissolved in low molar mass nematic solvents were determined via dynamic light scattering analysis. These results were compared to those of linear chains with similar chemical repeat structures. The nematic solvent used was 4′-pentyloxy-4-cyanobiphenyl (50CB). The cyclic LCP oligomers, Cy TPB10, have a mesogenic group, 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl) butane, separated by flexible decamethylene spacers. The twist viscosity of the cyclic Cy-TPB10 oligomers increases with molecular weight more strongly than the linear, TPB-10, suggesting that the hydrodynamic behavior of Cy-TPB10 is closer to that of a rigid rod than TPB10. Surprisingly, the intrinsic bend viscosity [η_bend] of Cy-TPB10 decreases with molecular weight, in contrast to the positive dependence for linear TPB10. This may reflect the higher strain energy in the smaller ring sizes. The hyperbranched LCP, TPD-b-8, is also based on the mesogen 10-bromo-1-(4-hydroxy-4′-biphenyl)-2(4-hydroxyphenyl) decane but with octyl groups at the chain ends. We compare the viscoelastic behavior of dilute nematic solutions of TPD-b-8 in 50CB against that of a linear main-chain LCP, TPB7, with the same mesogenic group but with heptamethylene spacers. The viscometric properties of TPD-b-8/50CB and TPB7/50CB are quite different. The results suggest that each chain is prolate (i. e., R_∥ > R_⊥) but that TPD-b-8 has a smaller chain anisotropy than that of TPB7. © 1995 John Wiley & Sons, Inc.     

Neutron scattering study and discussion of the backbone conformation in the nematic phase of a side chain polymer

A small angle neutron scattering study of a mesomorphic side chain polyacrylate in the nematic phase shows that the backbone adopts a prolate conformation. This observation is discussed in relation to the previous determinations of backbone anisotropy in the nematic phase of other side chain polymers. On the basis of the comparison with these previous determinations and also with the results obtained on other related systems, the assumption is made that, provided that the spacers are long enough, the natural tendency of the backbones is to adopt a prolate shape in any nematic phase devoid of smectic fluctuations.     

Transformation of a kinetically controlled nematic phase of a linear polymer into one which is thermodynamically controlled via cyclization [1]

The synthesis and characterization of cyclic main chain liquid-crystalline oligomers based on 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)butane (TPB) with 1,7-dibromoheptane (TPB-7(c)] are described. These oligomers were synthesized by the phase transfer catalysed polyetherification of TPB with 1,7-dibromoheptane under high dilution conditions and separated by column chromatography. Their cyclic structure was confirmed by 200 MHz ¹H NMR spectroscopy. The mesomorphic behaviour of TPB-7(c) was characterized by differential scanning calorimetry and polarized optical microscopy. The cyclic dimer is only crystalline, while the cyclic trimer, tetramer and pentamer exhibit an enantiotropic nematic mesophase. The high molecular weight linear homologue TPB-7(1) exhibits a nematic mesophase which has an isotropization transition temperature located in the very close proximity of its glass transition temperature. Therefore, this nematic phase is kinetically controlled. Due to the higher rigidity of cyclics versus linear structures the cyclic trimer, tetramer and pentamer exhibit higher isotropization transition temperatures than their linear homologue. Subsequently, the kinetically controlled nematic mesophase of the linear homologue is transformed into a thermodynamically controlled phase via cyclization.     

Topologically non-equivalent textures generated by the nematic electrohydrodynamics

Some classes of nematic liquid crystals can be driven through turbulent regimes when forced by an external electric field. In contrast to isotropic fluids, a turbulent nematic exhibits a transition to a stochastic regime that is characterised by a network of topological defects. We study the deformations arising after the electric field has been switched-off. In contrast to the turbulent regime, the relaxation of this topological-defect regime involves the annihilation of an interlacement of defect lines. We show that these defect lines separate regions of the nematic having topologically non-equivalent textures.     

Highly birefringent nematic and chiral nematic liquid crystals

We report a simple interference method to determine the dispersion of the extraordinary refractive index and birefringence of highly conjugated and coloured nematic liquid crystals used as light-emitting materials in organic electroluminescent devices. The measurements are made in the nematic glass phase at room temperature. The birefringence is highly dispersive and values up to 1.1 are obtained. Chiral groups are incorporated into the end chains giving a chiral nematic liquid crystal with a very wide stopband in the visible region. The Berreman matrix method is used to simulate transmission through the chiral nematic liquid crystal cell using the refractive index parameters obtained experimentally. Excellent agreement between theory and experiment is found.     

Highly birefringent nematic and chiral nematic liquid crystals

We report a simple interference method to determine the dispersion of the extraordinary refractive index and birefringence of highly conjugated and coloured nematic liquid crystals used as light‐emitting materials in organic electroluminescent devices. The measurements are made in the nematic glass phase at room temperature. The birefringence is highly dispersive and values up to 1.1 are obtained. Chiral groups are incorporated into the end chains giving a chiral nematic liquid crystal with a very wide stopband in the visible region. The Berreman matrix method is used to simulate transmission through the chiral nematic liquid crystal cell using the refractive index parameters obtained experimentally. Excellent agreement between theory and experiment is found.     

On the twist-bend nematic phase formed directly from the isotropic phase

The intriguing twist-bend nematic (N_TB) phase is formed, primarily, by liquid crystal dimers having odd spacers. Typically, the phase is preceded by a nematic (N) phase via a weak first-order transition. Our aim is to obtain dimers where the N_TB phase is formed directly from the isotropic (I) phase via a strong first-order phase transition. The analogy between such behaviour and that of the smectic A (SmA)–N–I sequence suggests that this new dimer will require a short spacer. This expectation is consistent with the prediction of a molecular field theory, since the decrease in the spacer length results in an increase in the molecular curvature. A vector of odd dimers based on benzoyloxybenzylidene mesogenic groups with terminal ethoxy groups has been synthesised with spacers composed of odd numbers of methylene groups. Spacers having 5, 7, 9 and 11 methylene groups are found to possess the conventional phase sequence N_TB–N–I; surprisingly, for the propane spacer, the N_TB phase is formed directly from the I phase. The properties of these dimers have been studied with care to ensure that the identification of the N_TB phase is reliable.     

Electrooptical properties of mesogenic chain molecules in solution and in nematic state

Electrooptical characteristics of mesogenic chain molecules in solution and in mesophase can be described in terms of intra- and intermolecular orientational orders. The value and sign of electric birefringence δn in a solution of kinetically rigid chain molecules are determined by the combination of two factors: intramolecular orientational order which depends on the dipolar and anisotropic architecture of the molecule and intermolecular orientational order caused by the action of the external electric field E. The value and sign of the dielectric anisotropy δε of the polymer nematic phase are also determined by the combination of intra- and intermolecular orders. However, in this case the latter is not maintained by the external field but by the nematic potential of the mesophase. Therefore, comparative investigations of electrooptical properties of polymers in solutions and in nematic melts make it possible to obtain information about the intra- and intermolecular orientational orders of the molecules under investigation in these two states. These investigations were carried out using the method of electric birefringence in solutions and the method of orientational deformations of nematic textures in an electric field. The objects being investigated were nematogenic dimers and trimers. Experimental data obtained for these compounds showed the presence of intramolecular order in their molecules, which is manifested in the odd-even oscillations of the value and sign of Kerr constant K≈δn/E² in solution and δε in the nematic phase when the number of C-C bonds in the methylene spacers of these molecules is varied. This effect is particularly dramatic in the mesophase where it is enhanced by intermolecular nematic potential.     

Inversion walls in homeotropic nematic and cholesteric layers

We describe the experimental properties of metastable domains associated with the presence of an Inversion Wall (IW ) and observed with homeotropically anchored nematic and cholesteric liquid crystals sandwiched between parallel glass plates. Such a distorted situation, stabilized by the application of an electric field parallel to the plates as described in reference [1], can also be obtained transiently either when filling a sample cell by capillarity or in some studies of directional solidification at the N-I interface [2]. The application of an electric field perpendicular to the plates with Delta epsilon 0 materials allows control of the reversal region thickness in the bulk of the sample and its associated birefringence. This IW can be stabilized in the particular case of low lateral extension globules in which the line tension of the looped disclination separating the pi wall regions from the homeotropic regions counterbalances the unfavourable bulk free energy. Particular attention is devoted to the defects of these walls, whose appearance using polarizing microscopy is similar to the umbilics of the Freedericksz transition. The structure of these 'four brush' defects is nevertheless here singular, corresponding to point defects of a 3D uniaxial nematic medium. In the case of a chiral nematic, these IW undergo a particular undulation instability which is also observed in 2D simulations.     

Landau theory for uniaxial nematic,biaxial nematic,uniaxial smectic-A,and biaxial smectic-A phases

We use the Landau theory of phase transitions to obtain the global phase diagram concerning the uniaxial nematic, biaxial nematic, uniaxial smectic-A and biaxial smectic-A phases. The transition between the biaxial nematic and biaxial smectic is continuous as well as the transition between the nematic phases and the transition between the smectic phases. The transition from uniaxial nematic and uniaxial smectic is continuous with a tricritical point. The tricritical point may be absent and the entire transition becomes continuous. The four phases meet at a tetracritical point.     

The temperature dependence of nematic liquid crystalline polymer melt diffusion

Polymer chain diffusion in the nematic mesophase was studied using a model main chain liquid crystalline (LC) polyether based on 2,2'-dimethyl-4,4'-dihydroxyazoxybenzene and mixed alkane spacers. A side chain LC polymethacrylate containing an azobenzene mesogenic group was also investigated. Tracer diffusion coefficients were determined as a function of temperature by an ion-beam depth profiling technique, forward recoil spectrometry. The results confirm that main chain LC polymer chain dynamics are dramatically affected by phase transitions and sample geometry. This behaviour is in marked contrast to the side chain LC polymer which exhibited no phase dependence on the part of the tracer diffusion coefficient.     

Spacer length dependence of TGBC* and SmA phases in cholesteryl and dihydrocholesteryl-containing trimer liquid crystals

Two series of trimer liquid crystals were investigated that contain a biphenylyl central group and two cholesteryl or dihydrocholesteryl terminal mesogenic groups. Only compounds with even spacers were investigated. The dihydrocholesteryl-containing trimers show a triply intercalated smectic A (SmA) phase when the spacer lengths are greater than 8, whereas the cholesteryl-containing trimers exhibit this triply intercalated SmA phase when the spacer lengths are more than 6. With shorter spacers, a twist grain boundary C* (TGBC*) phase was found. This is revealed by the formation of a typical dotted square grid pattern upon cooling from the chiral nematic (N*) phase in the planar texture. The dots are spaced by a distance of about 1.5-1.8 µm. Upon cooling from the N* phase in the focal conic texture a striped pattern is observed with the same spacing. X-ray diffraction revealed a repeat distance for the TGBC* phase that corresponds with a monolayer ordering. The results show that the weaker interaction between the dihydrocholesteryl groups compared with cholesteryl groups or longer spacers destabilize the monolayer TGBC* phase.     

The temperature dependence of nematic liquid crystalline polymer melt diffusion

Abstract

Polymer chain diffusion in the nematic mesophase was studied using a model main chain liquid crystalline (LC) polyether based on 2,2′-dimethyl-4,4′-dihydroxyazoxybenzene and mixed alkane spacers. A side chain LC polymethacrylate containing an azobenzene mesogenic group was also investigated. Tracer diffusion coefficients were determined as a function of temperature by an ion-beam depth profiling technique, forward recoil spectrometry. The results confirm that main chain LC polymer chain dynamics are dramatically affected by phase transitions and sample geometry. This behaviour is in marked contrast to the side chain LC polymer which exhibited no phase dependence on the part of the tracer diffusion coefficient.     

Computer simulations of nematic drops: coupling between drop shape and nematic order

We perform Monte Carlo computer simulations of nematic drops in equilibrium with their vapor using a Gay-Berne interaction between the rod-like molecules. To generate the drops, we initially perform NPT simulations close to the nematic-vapor coexistence region, allow the system to equilibrate and subsequently induce a sudden volume expansion, followed with NVT simulations. The resultant drops coexist with their vapor and are generally not spherical but elongated, have the rod-like particles tangentially aligned at the surface and an overall nematic orientation along the main axis of the drop. We find that the drop eccentricity increases with increasing molecular elongation, κ. For small κ the nematic texture in the drop is bipolar with two surface defects, or boojums, maximizing their distance along this same axis. For sufficiently high κ, the shape of the drop becomes singular in the vicinity of the defects, and there is a crossover to an almost homogeneous texture; this reflects a transition from a spheroidal to a spindle-like drop.     

The elasticity of nematic networks

Nematic rubbers are composed of crosslinked polymer chains with stiff rods either incorporated into their backbones or pendant as side chains. When nematic effects axe strong, such rubbers exhibit discontinuous stress-strain relationships and spontaneous shape changes. We model such a rubber using Gaussian elasticity theory, including the nematic interaction via a mean field. Results are presented for the cases of uniaxial extension and compression. Under uniaxial extension the rubber can undergo a first order phase transition to a uniaxial nematic phase. Under uniaxial compression first or second order transitions are possible to genuinely biaxial nematic states with biaxial strains. When nematic effects are very small (i.e. T >> T_c where T_c is the nematic-isotropic phase transition temperature of the rubber) we postulate that the model is a good approximation to a conventional, non-nematic elastomer, and fit our model to data from an isoprene rubber.     

Rod-shaped dopants for flexoelectric nematic mixtures

We report the synthesis and liquid crystalline behaviour of two series of para-substituted terphenyls as dopants with a rigid rod-like shape, rather than a wedge-, pear- or banana-shape, for guest–host nematic mixtures with flexoelectric properties. One series of liquid crystalline dopants is of low-to-strongly negative dielectric anisotropy and the other is of low-to-strongly positive dielectric anisotropy. The usefulness of apolar and polar rod-like dopants as components of flexoelectric nematic mixtures of positive dielectric anisotropy for use in LCDs is investigated in general and the dependence of the flexoelectric properties of the doped nematic mixtures on the polarity of the dopants is studied in particular. The correlation between the concentration of the dopant and the magnitude of the flexoelastic ratio of several guest–host nematic mixtures is investigated.     

Determination of the permittivity of nematic liquid crystals in the microwave region

Two 3 mm thick microscope glass plates, having one face plus their two long edges coated by a thick metallic film, are spaced 75 μm apart by mylar spacers. Because of the metallic coatings on the inner faces the structure acts as a single metallic slit. The space between the two coated plates is filled with aligned nematic liquid crystal (E7, Merck/BDH) and the cell is inserted in an absorber aperture. This single metallic slit geometry supports resonant modes when microwaves are incident with their polarization (E-field) perpendicular to the slit. The structure gives a set of Fabry-Perot-like resonant transmission frequencies. These frequencies move when a voltage is applied between the two plates, the liquid crystal being first aligned homogeneously, then realigning homeotropically with the applied field. By minotoring these changes a fast and easy to use procedure for determining the permittivity and its anisotropy for nematic liquid crystals in the microwave region has been developed. The parameters determined for E7 are ε_e = 3.17 (n_e = 1.78 ± 0.01) and ε_o = 2.72 (n_o = 1.65 ± 0.01), (Δn ≈ 0.13) in the 40.0–60.0 GHz region.