X-Ray Diffraction by Liquid Crystals

Following a very brief historical review, x-ray diffraction by nematic and smectic liquid crystals is critically examined in terms of the data available and the structural models and molecular theories that have been proposed to explain it. Studiesof TBBA are used to illustrate some of the principal mesophases that have been distinguished. Other types of liquid crystals and their phase transitions are also briefly reviewed.

This analysis shows that careful experimental work is still needed to decide the kinds of models that best describe the various types of mesophases that have been shown to exist.     

Critical Points and Re-Entrance in Liquid Crystalline Side-Chain Polymers

Competing nematic and smectic A phases of comb-like polymers are described by combining Maier-Saupe and McMillan type theories with the worm concept of semi-flexible polymers. There are as few material parameters as possible: main chain flexibility and phenomenological coupling constants. New qualitative predictions, the existence of critical points and re-entrant nematic phases, as well as quantitative predictions for comparison with experiments are provided. A new mechanism for thermotropic nematic biaxiality which is specific of side-chain polymeric liquid crystals is found.     

Simultaneous X-Ray Diffraction and Differential Scanning Calorimetry (XDDSC) in Studies of Molecular and Liquid Crystals

The technique of simultaneous X-ray diffraction and differential scanning calorimetry (XDDSC) is introduced into the field of molecular and liquid crystals. The technique allows fast time-resolved X-ray diffractograms to be recorded simultaneously with the recording of heat flow into or out of the specimen during a heating, cooling or isothermal scan. Structural transformations, as revealed by changes in the diffraction pattern, can thereby be unambiguously correlated with thermal events such as endo-or exo-therms or changes in heat capacity. Small and wide angle diffraction can be monitored. Sample pans and cuvettes made of boron nitride or graphite are used, both materials combining high transparency for X-rays with good thermal conductivity. Selected examples of application of the technique are presented.     

Kerr Effect Studies in Liquid Crystalline Substances

The static and dynamic pretransitional behaviour was investigated by the electric Kerr effect in three nematic substances above the clearing point. The measured Kerr constants exceed that of nitrobenzene by more than a factor of 50…︁ 80 which are due mainly to pretransition phenomena and the strong dipole moments of the compounds. A formula is given for the calculation of the Kerr constant. The latent heat at the nematic-isotropic phase transition calculated from the temperature dependence of the Kerr constant by means of the Landau theory is in good agreement with the experimental values. Size and relaxation behaviour of pseudonematic domains are determined by Kerr effect measurements.     

Raman Scattering and X-Ray Diffraction Studies on Alkali-Metal Intercalated Clays

Abstract

Vermiculite and fluor-tetrasilicic mica were intercalated with alkali metals (Na, K and Rb) by vapor transport. X-ray and Raman scattering experiments were conducted to study the structure and lattice dynamics of the new clay compounds. When Rb and K atoms were intercalated to the host materials, superlattices were formed. In Na intercalated compounds, however, no superlattice x-ray diffraction peaks were found. Raman spectra exhibited drastic changes after alkali-metal intercalation, reflecting the structural changes found by our x-ray diffraction.     

Physical Characterization of Blends Based on Liquid Crystalline Polyesters and Amorphous Polymers

In this work the effect of the inclusion of low percentages of theliquid crystal polymer PET/PHBGO on the rheological and mechanical behaviour of Polycarbonate is described.     

Rheo-Optical Studies of Liquid Crystalline Solutions of Helical Polypeptides

The shear dependence of structures of liquid crystalline solutions of Poly-γ-benzyl-l-glutamate PBLG in m-cresol was examined in a polarizing microscope using a specially constructed shearing stage and stroboscopic illumination. Three different textures were observed depending on shear rate. The shear rates at which the texture changes occurred correlated well with the changes in sign of the first normal stress difference reported earlier.^1,2 The region of negative first normal stress difference corresponded to a texture consisting of striations perpendicular to shear.

The transverse striations were also observed to develop over a period of seconds or minutes after cessation of shear at rates within the first positive region of N ₁, These striations could be fixed in a dried film by using a volatile helicogenic solvent (1,4-dioxane).

A speculative model is proposed to account for the rheological observations in Refs.^1,2 and the rheo-optical observations reported herein.     

X-Ray Diffraction Studies on Point Defects in II–VI Compounds

The point defect concentration in Te-rich CdTe and Hg_1-xCd_xTe annealed at various temperatures has been estimated from precision lattice parameters using a simple continuum inclusion model and compared with densities of electrically charged defects determined by high-temperature Hall and conductivity measurements. The nonstoichiometry is realized by cation vacancies. Dependent on the CdTe content, the ratio of total to charged defect concentrations varies between about unity for HgTe-rich composition and 75 for CdTe. Therefore, it is necessary to distinct between “electrical” and “chemical” stability regions.     

The Use of X-Ray Diffraction in the Study of Thermotropic Liquid Crystals With Rod-Like Molecules

The paper first reviews briefly the various kinds of information that can be obtained from x-ray diffraction studies. Next, specific examples are given from the literature of determinations of each of the different kinds of data.     

Methods of Coherent X-Ray Diffraction Imaging

Crystallography Reports - Methods of coherent X-ray diffraction imaging of the spatial structure of noncrystalline objects and nanocrystals (nanostructures) are considered. Particular attention is...     

Experimental Investigations of the Conditions for the Formation of the Liquid Crystalline State of Polymers

The diagrams of state for concentrated PBG solution in coordinates relating volume fraction-geometric asymmetry and volume fraction-temperature are investigated. The order parameter for macromolecules in the anisortropic phase is dettermined. The experimental data compare with the existing theoretical models for th formation of the liquid crystalline state in solutions of stiff polymer molecule. It is shown that experimental data are in good quantitative agreement with the Flory's lattice model.     

Thermotropic Liquid Crystalline Compounds with Lateral Long Chain Substituents (VII). X-Ray Studies in 1,4-Bis-(4-n-oetyloxybenzyoloxy)-2-n-alkylbenzenes

X-ray studies in substances with the general formula in the nematic states were performed. The results prove the existence of cybotactic groups despite the fact that the branched substances do not show smectogenic properties. We propose a model for the packing of the molecules, which explains the influence of the lengths of the lateral branches on the structure of the cybotactic groups.     

Liquid Crystalline Catalysis, 31, Monomolecular Rearrangements of Terpene Derivatives in Liquid Crystalline Solvents

The ability of limonene and linalool to rearrange in mesomorphic media is apparently determined by the constraints exerted by the solvent structure on the translational diffusions of the reactant solute molecules. Selective conversions seem to be promoted by the different media. Alkylcyclohexyl- and alkylbicyclohexyl-carboxylic acids and their mixtures with toluic acid have been used as solvents. The B structure of their smectic phases has been demonstrated by X-ray diffraction studies.     

Investigation of the Cholesteryl Oleate Mesophases by X-Ray Diffraction

The following phase transitions occurring in the cholesteryl oleate were investigated by X-ray diffraction: solid-isotropic liquid, isotropic liquid-cholesteric, cholesteric-smectic.

The sample purity was 98%. Strong pretransitional effects were observed at the solid-isotropic liquid phase transition and at the cholesteric-smectic phase transition.

At this last transition the longitudinal coherence length ξ_∥ appears to diverge as the critical temperature is approached in the cholesteric phase, whereas the transversal coherence length ξ_τ increases at the critical temperature in the smectic phase in an abrupt way. It seems from the temperature dependence analysis of the angular position of the low angle peak that the smectic phase is a smectic A phase and that a progressive melting of chains occurs at the temperature increases.     

Erratum to:Methods of Coherent X-Ray Diffraction Imaging

Crystallography Reports - An Erratum to this paper has been published: https://doi.org/10.1134/S106377452134006X     

Quantum Chemical,Spectroscopic, and X-Ray Diffraction Studies of N-diphenylphosphino-4-methylpiperidine Selenide (1)

The title molecule, N-diphenylphosphino-4-methylpiperidine selenide(1), was prepared and characterized by elemental analysis, ¹H-NMR, ³¹P-{¹H} NMR, IR, and X-ray single-crystal determination. The compound crystallizes in the monoclinic space group P 2₁/c. In addition to the molecular geometry from X-ray determination, vibrational frequencies and gauge, including atomic orbital (GIAO) ¹H- and ³¹P-{¹H} NMR chemical shift values of the title compound (1) in the ground state, were calculated using the Hartree–Fock and density functional methods with the 6-31G(d, p) basis set. The calculated results show that the optimized geometries can well reproduce the crystal structures. Besides, the theoretical vibrational frequencies and chemical shift values show good agreement with experimental values. The predicted nonlinear optical (NLO) properties of the title compound are greater than those of urea. In addition, density functional theory (DFT) calculations of the molecular electrostatic potentials (MEPs), frontier molecular orbitals (FMOs) of the title compound were carried out at the B3LYP/6-31G(d) level of theory.     

Formation of a Banded Texture in Solutions of Liquid Crystalline Polymers: 1. Hydroxypropylcellulose in H2O

Abstract

The formation of a banded texture was investigated for sheared anisotropic solutions of hydroxypropylcellulose (HPC) in H₂O. A cone and plate rheometer made of highly polished glass allowed the exploration of the shear rate (γ) range between 0.1 and 150 sec^?1 and the study of the effect of shear time t_s. Texture, monitored with a video-camera, appeared after a time t_b following cessation of shear. t_b is usually a decreasing function of γ and t_s. In most cases a precursor banded texture precedes the banded texture, and t_b attains zero at high enough γ or t_s. However, when a particularly good orientation of the flowing solution is achieved, the precursor texture is not observed, t_b is finite, and the bands are particularly well formed. We speculate that bands are the normal relaxation mode for well oriented solution. For less oriented solutions flow instability may lead to bands even during flow.     

Dynamic Layer Response under Electric Field in Antiferroelectric Liquid Crystal Cells Measured by Synchrotron Microbeam Time Resolved X-Ray Diffraction

Abstract

Direct observation of the local layer response of an antiferroelectric liquid crystal to the step form electric field has been carried out by a time resolved synchrotron X-ray micro diffraction measurement. When an electric field was changed from high voltage to OV, corresponding to the ferroelectric to antiferroelectric phase transition, the local layer transformed from the bookshelf to the quasi-bookshelf structure within 0.3 ms. The horizontal chevron structure was found in both the phases, though the decrease in the horizontal chevron angle was observed during a period of 0.2 ms after turning off the electric field. In the antiferroelectric to ferroelectric phase transition process (from OV to high voltage), the layer structure transformed to the bookshelf within 0.04 ms.