Structure Effect of Solute on Orientational Order in Binary Mixture by 2H-NMR and Molecular Simulations

Abstract

The orientational order parameters of six solutes with different shapes and sizes dissolved in two nematic solvents have been measured as a function of temperature. The parameter, S^xx-S^yy is correlated with the molecular geometrical structure, while S^zz is affected by not only the geometry but also the anisotropy in the polarizability. The molecular dynamics simulations are carried out using a realistic atom-atom potential for evaluating the ordering properties in the nematic phase. The results provide reasonable values of S^zz corresponding to experimental ones for solutes and solvents, and also a prediction of uniaxiality for the nematic phase.     

Synthesis,Characterization and Mesomorphic Properties of New Rod-like Thiophene Based Liquid Crystals

Two new mesogenic homologous series of Schiff base esters, 2-[4-(4′-n-Alkoxy benzoyloxy) benzylidenamino] 3-cyno thiophine (Series-A) and Schiff base cinnamates, 2-[4-(4′-n-alkoxy cinnamoyloxy) benzylidenamino] 3-cyano thiophene (Series-B), comprising a thiophene moiety were synthesized. Structural elucidation was carried out using elemental analysis and spectroscopic techniques such as FT-IR, ¹H-NMR and ¹³C-NMR, and mass spectrometry. The mesomorphic properties and thermal stabilities of the title compounds were studied by using differential scanning calorimetry and optical polarizing microscopy. All the derivatives are mesomorphic in nature showing the nematic phase, and the higher members of Series-A show a smectic C phase whereas Series-B exhibits only the nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related compounds.     

Material Highlights: Liquid Crystal Polymers

Abstract

A key issue in the area of side chain liquid crystal polymers concerns the conformation of the backbone within the mesophase. In order to resolve this matter, Noirez and co-workers (Liquid Crystals, 1995, 18 129) have studied a wide range of polymers exhibiting both nematic and smectic behaviour using small angle neutron scattering. Their results combined with a survey of those in the literature reveal that if the polymer is solely nematogenic, then the backbone adopts a prolate conformation in which on average it lies along the director. By contrast, in a smectic phase the backbone adopts an oblate shape and on average lies perpendicularly with respect to the director. This arises from a microphase separation in which the backbones are distributed between the mesogenic layers. However, the backbones can cross the mesogenic layers although their ability t o do so depends on, amongst other factors, the degree of polymerization. If the polymer exhibits both nematic and smectic behaviour, then in the nematic phase the backbone adopts a slightly oblate shape resulting from smectic fluctuations.     

The Study of the Charge Carrier Transport in Nematic Mixtures

Abstract

The electrical conductivity and the mobility measurements in nematic mixtures Merck 5 and Merck 7a are reported. The drift mobility of carriers about 10^?5 cm²/Vs at room temperature was determined. Identical activation energies of conductivity and mobility were obtained (0.4 eV for Merck 7a and 0.3 eV for Merck 5). In our opinion, the conductivity of examined mixtures is controlled by ionic transport.     

ENHANCED FLEXOELECTRIC SWITCHING BEHAVIOUR IN THE CHIRAL NEMATIC PHASE

Abstract

In order to develop materials that exhibit enhanced flexoelectric switching in the chiral nematic phase we have identified mesogenic units that display inherently strong flexoelectric coupling capabilities. Here we examine the oxycyanobiphenyl (OCB) moiety: homologues from the nOCB series exhibit significant electro-optic switching effects when doped with a highly chiral additive. Here we have examined lower dielectric anisotropy materials, since they allow the flexoelectric response to be extended to high field amplitudes. We show that dielectric coupling strength can be low in symmetric bimesogenic molecules. The flexoelectric response of such a molecular structure is tested by doping a homologue from the series CBOnOCB with a chiral additive: very significantly we find that the optic axis is rotated through 2φ = 45° in < 50 μs on reversing the polarity of the field (amplitude E = ±6 V μm^?1). Subsequently we have synthesized room temperature chiral nematic materials that exhibit 2φ > 90° at E = 10 V μ^?1.     

Nematic Thiophenes for STN-LCDS and Flexoelectric LCDS

Abstract

We report anew class of liquid crystals incorporating a 2,5-disubstituted thiophene ring and one or two conjugated trans-carbon-carbon double bonds in the terminal chain for use as components of nematic mixtures for TN-LCDs and STN-LCDs. The combination of these molecular elements contribute towards generating a high birefringence, a high nematic clearing point as well as a low viscosity for these materials. Several of these compounds exhibit a melting point below room temperature. This is the first time a room temperature nematic phase has been reported for phenyl thiophene derivatives. The new thiophene compounds can be used to induce a high birefringence in nematic mixtures for LCDs with short response times.     

Conoscopic image of a biaxial nematic phase in a sodium decyl sulfate – decanol – D2O mixture

ABSTRACT

The nematic phases of a lyotropic system NadS/ decanol/ heavy water are investigated using optical conoscopy and image processing. The phase diagram obtained from these lyotropic materials predicts the occurrence of a direct phase transition, which does not present the biaxial nematic phase, between the discotic (N_D) and calamitic (N_C) nematic phases. A biaxial nematic (N_B) phase is optically characterized and confirmed through conoscopic image, inside the biaxial range, between the two uniaxial nematic phases. Also, their respective transition points are determined by means of image processing. The N_B phase observed here is discussed as part of the nature of the micellar configuration of lyotropic materials which exhibit uniaxial nematic phases.     

An optical microscopy study of the biaxial ‐ calamitic nematic lyotropic phase transition

Lyotropic nematic textures are investigated, using optical microscopy, near the reentrant isotropic (I_RE) ‐ discotic nematic (N_D^‐) ‐ biaxial nematic (N_B) ‐ calamitic nematic (N_C⁺) ‐ isotropic (I) phase transitions in a lyotropic mixture of potassium laurate, decanol and D₂O. The N_B, intermediate phase between the two uniaxial nematic ones, is characterized by optical birefringence measurements. In this way, using a polarizing microscope and a colour CCD digital camera, the N_B – N_C⁺ phase transition is identified as well as the domain of the N_B phase and N_D^‐ – N_B transition point in accordance with optical birefringence data (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

POLYMERIZATION-INDUCED PHASE SEPARATION OF POLYMER-DISPERSED LIQUID CRYSTAL

Abstract

Polymerization-induced phase separation in polymer-dispersed liquid crystal is studied by computer simulations in two dimensions. The domain morphology resulting from phase separation is investigated by solving the couple set of equations for the local volume fraction and the nematic order parameter, taking into account the viscoelastic effects and gelation due to polymerization. Comparing the morphology of phase separation by temperature quench, it is shown that the viscoelastic effects and gelation enable the polymer-rich phase to form a stable interconnected domain even when the polymer component is minority.     

Synthesis and Mesomorphic Characterisation of Chiral Homologues

Abstract

Chiral liquid crystals have attracted considerable interest as they exhibit a good variety of modulated phases. We have synthesised a homologous series viz., 4-(4^!-n-alkoxy benzoyloxy) benzylidene-4^!!?1-(s)-methyl propoxy anilines, incorporating a terminal chiral centre, inorder to obtain better understanding of the relationship between molecular structure and appearance of SmC* phase in the molecules. It is observed that, in the present series the lower members upto butyl are pure nematogens, while pentyl to hexadecyl derivatives exhibit classical smectic as well as nematic mesophases. An additional smectic C* phase is observed in the middle octyl to dodecyl homologues. The homologues have been characterised by IR, NMR and DSC. Their mesomorphic properties have been compared with structurally related homologous series.     

The Structure of Lyotropic Nematic Decylammoniumchloride and Bromide Systems by PMR of Monomethyltin Complexes and by Microscopic Studies

The pmr spectrum of methyltintrichloride in aqueous micellar solutions of decylammoniumchloride and KCl, and of decylammoniumbromide and KBr was investigated. The large scalar SnH couplings of 134.0 Hz and 130.2 Hz respectively indicate the formation of six coordination complexes CH₃SnCl₅ ^{- -} and CH₃SnBr₅ ^{- -} in the micellar solutions, but the geometrical structure of the CH₃Sn moiety is little affected by the complex formation. The complexes orient with their symmetry axis preferably parallel to the nematic axis.

In microscopic studies on selected mixtures a reversible first order phase transition was observed between nematic and isotropic micellar solution at about 45°C and a reversible transition between a lamellar smectic phase and the nematic phase at about 30°C that appears to be of second order. The optical observations and the orientation of the methyltin complex indicate that the nematic solutions have micelles of a bilayer structure.     

X-ray diffraction study of p -(alkoxybenzylidene)- p ′-toluidines C5H11O-C6H4-CH=N-C6H4-CH3 and C8H17O-C6H4-CH=N-C6H4-CH3

The molecular and crystal structures of two p-(alkoxybenzylidene)-p′-toluidines C₅H₁₁O-C₆H₄-CH=N-C₆H₄-CH₃ (1) and C₈H₁₇O-C₆H₄-CH=N-C₆H₄-CH₃ (2), which form the nematic phase upon melting, is determined by X-ray diffraction. The geometry of the benzylideneaniline fragments in molecules 1 and 2 is actually identical. The crystal packings of 1 and 2 are characterized by the alternation of layers formed by loosely packed aliphatic fragments of molecules and layers of closely packed aromatic fragments. The packing in the aromatic regions of 1 follows the parquet pattern. The crystal packing of 2 has a stacking structure, which is formed by π-stacking dimers superimposed on one another. The formation of the mesogenic phase upon melting of crystals 1 is due to the disturbance of the structurality of loose aliphatic layers with retention of the structure of the aromatic regions, which are stabilized by the cooperative effect of weak directed C-H ··· π-system interactions. The mesogenic phase of crystals 2 is formed upon melting as a consequence of the retention of the structure of π-stacking dimers. Original Russian Text ? L.G. Kuz’mina, N.S. Kucherepa, M.N. Rodnikova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 6, pp. 1079–1085.     

Surface and Magnetic Orientation in a Type II Nematic Lyomesophase

Abstract

A type II nematic lyomesophase formed by a quaternary system (K decanoate/water/decanol/KCI) has been studied by X-ray diffraction (XD) and optical microscopy (OM) at room temperature. Samples in capillaries of various thicknesses, materials and geometries have been studied under the influence of wall effects, residual magnetic orientation and orientation in presence of magnetic fields. Results evidence that surface orientation extend typically up to 0.5 mm. The planar diffracting units have a characteristic distance in the director direction of 36 Å. The analysis of the compromise between surface and magnetic orientation by XD allowed to determine a critical field of 200 G for a 0.5 mm thickness; the elastic constant is estimated as 10^?-⁷ dynes. Analised by OM, the sample is axially positive, but shows also a weak biaxiality.     

Cluster self-organization of intermetallic systems: Quasi-spherical nanocluster precursors with internal Friauf polyhedra (A-172) and icosahedra (B-137) in the Li19Na8Ba15 (hP842) crystal structure

A combinatorial and topological analysis of Li₁₉Na₈Ba₁₅ (hP842, a = 20 ?, c = 93 ?, V = 33552 ?³, P $ \bar 3 $ \bar 3 ) has been performed using computer methods (the TOPOS program package). Two types of crystal-forming quasi-spherical nanoclusters about 20 ? in diameter with internal Friauf polyhedra (A-172) and icosahedra (B-137) have been established by the complete decomposition of the 3D factor graph of the structure into cluster substructures. Each type of nanoclusters forms close-packed 2D layers 3⁶, which alternate along the c axis. The B-137 and A-172 nanoclusters are composed of three layers and have shell compositions (1 + 12 + 32 + 92) and (1 + 16 + 59 + 103) with local symmetries 3 and $ \bar 3 $ \bar 3 , respectively; they were revealed for the first time in crystal structures as cluster precursors. The icosahedral B-137 nanocluster contains a 104-atom quasicrystal approximant (Samson cluster).     

Crystal Structure of a Non-Conductive Non-Stoichiometric Tetrathiafulvalenium Salt: (TTF)3(BF4)2

Abstract

(TTF)₃(BF₄)₂ crystallizes in the triclinic system, space group P1, a = 8.017(3), b = 8.601(1), c = 11.635(2) Å, α = 108.79(1), β = 100.96(2), γ = 99.09(2)°, Z = 1. The TTF entities are stacked in parallel columns arranged into parallel layers alternating with layers of BF₄ ^? anions. A TTF stack is constituted of (TTF⁺)₂ diads interspersed with TTF° monads; the TTF⁺-TTF⁺ overlap is of the ring-over-ring type while the TTF⁺-TTF⁺ overlap is of the bond-over-ring type. These features explain the low conductivity ([sgrave]_powdcr = 2 × 10^?5 Ω^?l cm^?1) of this apparently non-stoichiometric TTF salt.     

Market Trends for Flat Panel Displays

Abstract

Arecent report from Stanford Resources entitled ‘Flat Panel Monitor Market Trends 1988’ presents a realistic forecast for the FPD market, which is expected to reach a shipment value of $4 billion in the year 2000. The Flat Panel Display market covers active matrix twisted nematic displays (TFT-LCD) and matrix-addressed super-twisted nematic displays (STN-LCD), and the following are highlights from the market analysis and forecasts.     

The Orientational Optical Non-Linearity of Liquid Crystals

Abstract

The cubic optical non-linearity of a cholesteric liquid crystal (CLC) having a planar helical texture is considered. A study was made of an effect which has a minimal establishment time and is due to the change in the director distribution along the helix under the orientational influence of the light field. Polarisation peculiarities of the non-linearity, when the light wave propagates along the helical axis, are discussed. Self-focusing should not occur for circulary polarised light, but has the constant ?₂ ～ 8.10^?8 cm³/erg for linearly polarised light. The additional rotation of the axes of elliptical polarisation is predicted to be proportional to the light intensity and determined by the same constant ?₂; this rotation is identical for both right-and left-handed CLC. Non-linear optical activity is absent in the approximation under consideration.

Analogous effects for light propagating through an oriented nematic are discussed.     

NMR and X-ray Investigations of a Plastic Crystalline Phase in MBBA

Abstract

Wideline and high resolution NMR studies have been carried out on MBBA in its isotropic, nematic and solid phases. Isotropic and nematic phase spectra correspond to what has been reported earlier. In the solid phase, contrary to expectations, very intense narrow signals similar to signals of the isotropic phase have been observed for the first time at temperatures close to the solid ? nematic phase transition temperature. This indicates rapid reorientational or translational motion in the system. The X-ray results however confirm the existence of translational order. The results are interpreted as indicative of the existence of a plastic crystalline phase in MBBA.     

Synthesis,structure, and mesomorphism of novel liquid crystalline acrylate monomers and polymers

A series of novel liquid crystalline monomers (M₁?M₈) and side chain polymers base polyacrylate backbone were synthesized. The chemical structures were characterized by FT-IR and ¹H-NMR spectra. The mesomorphism and thermal behavior was investigated by polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis. The relationships of structure and mesomorphism are discussed in detail. The eight monomers and their corresponding polymers all show enantiotropic nematic phase. With increasing the spacer length or flexibility of the terminal group, the melting temperature (T_m) and isotropic temperature (T_i) of the corresponding monomers and polymers all decreased. However, with increasing the rigidity of the mesogenic core, T_m and T_i of the corresponding monomers and polymers all increased. TGA showed that all the polymers obtained in this study had excellent thermal stability.     

Orientational Order Parameter in 1-Hexyl-4-(4-Isothiocyanatophenyl) Bicyclo [2,2,2] Octane using X-Rays

Abstract

1-Hexy1-4-(4-isothiocyanatophenyl)bicyclo[2,2,2]octane (HIPBO), a nematic liquid crystal which shows nematic phase in the temperature range 52.8 to 90.2°C, has been used along with imaging plate system to record X-ray Laue type diffraction pattern at different temperatures. For this purpose oriented sample was used. Orientational order parameter was obtained using Fourier method, recently reported by us, and has been compared with that of other existing methods.