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.     

Lithium Transport Through Sputter Deposited Lithium Cobalt Dioxide Thin Film Electrode

Abstract

Lithium transport through lithium cobalt dioxide thin film electrode prepared by rf-magnetron sputtering was investigated in IM solution of LiClO₄ in propylene carbonate using cyclic voltammetry, galvanostatic intermittent titration technique (GITT) and potentiostatic current transient technique. The cathodic and anodic current transients exhibited the non-Fickian behaviour of lithium transport when the applied potential steps encountered potential plateaus near 3.91 V _Li/Li+' determined from GITT. It is suggested that the occurrence of this abnormal behaviour during lithium intercalation and deintercalation is accompanied by a ‘diffusion-controlled’ α/β phase transformation and ‘cell-impedance-controlled’ phase transformation, respectively. Lithium transport through the electrode comprising two phases of α and β has been theoretically considered by a numerical analysis of the phase transformation.     

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.     

Magnetic Field Dependence of Laser Light Scattering through CBOOA in Nematic Phase

In the nematic phase of homeotropically aligned liquid crystals which have the smectic A phase at lower temperature, interference rings have been observed above some threshold magnetic field H_c which nearly coincides with the ocurrence of Freedericksz transition, only for the light polarized parallel to the direction of magnetic field. This interference ring disappears with increasing magnetic field above second threshold H_s . The origin of these interference rings is explained tentatively by a periodic deformation of bulk directors.

The bend elastic constant of CBOOA estimated from the measurements of the interference ring as a function of temperature, diverges with the critical exponent (0.5 ± 0.02) near the smectic A-nematic transition temperature and agrees well with a recent suggestion of McMillan based on the mean field theory.     

Structural Analysis of the Layered Compounds Cu x TiS2

Abstract

A structural analysis of single crystals of the layered compounds Cu _x TiS₂ (x=0. 0.21 and 0.38), which were prepared by the iodine transport and the electrochemical methods, has been performed by X-ray diffraction. The displacement parameters of Ti and S atoms along the c axis are larger than those along the a axis. It is understood that the intra-layer bonding between Ti-Ti and S-S atoms is stronger than the inter-layer bonding between Ti-and S-layers. Both distances between Ti-and S-layers and between Cu-and S-layers are enlarged without changing the structure of the mother phase after intercalating Cu atoms.     

Structure of Fullerene Anchored by Five-Membered-Ring

Abstract

The X-ray crystal structure of propanofullerene derivative 1 obtained by [3+2] cycloaddition has been determined by X-ray analysis.     

WO3-based electrochromic system with hybrid organic–inorganic gel electrolytes

Thin metal oxide films for a WO₃-based symmetric electrochromic system with a nickel oxide layer as the counter electrode have been prepared by spray pyrolysis on SnO₂:F coated soda-lime float glass, at a temperature of 670–720 °C and using metal acetylacetonates as precursors. The films have been characterized for composition and morphology by scanning electron microscopy equipped with an X-ray energy dispersive analyzer (SEM/EDAX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Electrochromic properties have been examined in the electrochemical cells of a smart window arrangement using lithium ion doped sol–gel derived organic–inorganic hybrid materials as electrolytes. Hybrids with room-temperature ionic conductivities of 10^?4–10^?3 Ω^?1 cm^?1 have been synthesized from tetraethyl orthosilicate (TEOS) with an addition of 35 mass % of organic compounds. Coloration-bleaching of WO₃ films with lithium ions from hybrid electrolytes has resulted in the desired modulating the properties in the visible and near infrared spectrum range. An XPS analysis has shown the presence of a lower oxidized tungsten oxide phase (WO_2.92) in the WO₃ film.     

Structural Phase Transition of an Intercalation Compound Mn1/4NbS2

Abstract

A structural phase transition of an intercalation compound Mn_1/4NbS₂ has been investigated by X-ray diffraction at high temperatures. The lattice parameter c exhibited a discontinuous change at 640K. The superlattice reflections observed below 640K disappeared suddenly above 640K. The phase transition at 640K took an aspect of the first-order phase transition. The precise structure analyses were performed at various temperatures above and below the phase-transition temperature. It was revealed that Mn atoms were arranged in disorder in the high-temperature phase, while the Mn atoms were ordered forming the 2a ₀ × 2a ₀ × c ₀ superlattice in the low-temperature phase. The Nb and S atoms around the ordered Mn atoms slightly shifted from the high-symmetry position in the low-temperature phase. The order parameters were the degree of order of the Mn atoms and the degree of displacement of the Nb and S atoms.     

Study of the structural features of ε-Co nanoparticles synthesized by cobalt carbonyl decomposition in the presence of surfactant

Cobalt nanoparticles (3–7 nm in size) obtained by cobalt carbonyl decomposition in 1,2-dichlorobenzene in the presence of surfactants (trioctylphosphine oxide and oleic acid) have been studied by a complex of structural methods: small-angle X-ray scattering, electron diffraction, and transmission electron microscopy. The nanoparticles synthesized are found to consist of the cubic ε-Со phase; their crystal structure is described within the sp. gr. P4₁32, a = 6.097 Å. Using small-angle X-ray scattering, the size and shape of nanoparticles have been determined directly in the liquid dispersion. Most of the particles have a spherical shape; their average size is ≈3.5 ± 0.5 nm, which agrees with the electron microscopy data. Possible factors causing the ε-phase formation during synthesis of metallic Co nanoparticles are discussed.

     

High-temperature phase transition in ferroelastic K2Ba(NO2)4

X-ray diffraction studies of K₂Ba(NO₂)₄ crystals were performed in the vicinity of the paraelastic-ferroelastic phase transition. The structural parameters and the behavior of the spontaneous deformation near the phase transition were determined. The experimental data were analyzed based on a phenomenological theory. It was shown that the high-temperature phase transition is of the first order.     

Phase Transitions in Chlorobenzene-Cis-Decalin Mixtures: A Nuclear Magnetic Resonance,Thermal Analysis and Phase Diagram Study

Using nuclear magnetic resonance and differential scanning calorimetry we have been able to observe the molecular rotation properties of chlorobenzene-cis-decalin mixtures in their glassy, amorphous and crystalline phases. The results indicate: that in “rapidly” cooled samples the behavior of the host dominates the properties of the mixtures; that reorientation of the guest molecule is less restricted in the amorphous phase than in the glassy phase; that when the material crystallizes from the amorphous phase on warming, reorientation again becomes severely restricted. The temperatures at which these phenomena occur agree with the phase diagram that has been determined for these materials. Similar experiments on t butyl chloride-cis-decalin mixtures support the above conclusions. These conclusions are in agreement with the previous dielectric studies.

Our magnetic resonance and thermal analysis experiments support the argument that the behavior of the CD host dominates the behavior of guest polar molecules in rapidly cooled mixtures. At the lowest temperature (110 K) CD forms a glassy phase unaccompanied by any heat of crystallization. On warming this glassy phase transforms near 150 K to an amorphous phase where considerable motion of both host and guest molecules occurs. Above 160 K the material crystallizes and reorientation is once again severely restricted up to the eutectic melting of 210 K. There appears to be no time dependence to these transformations and, as long as one stays below the crystallization temperature, the glassy-amorphous transition is reversible.     

Investigation of the structure and mechanisms of thermal motion in nanostructured undecylenic acid

Abstract

We have compared the structure, phase transitions and the thermal motion mechanisms of the undecylenic acid in bulk and inside a porous matrix using powder X-ray diffraction, calorimetry and IR-spectroscopy methods. The matrix used was a porous silicon with cylindrical pores (D?=?20?nm). The interaction between the walls of the porous silicon and the nanocrystals of the undecylenic acid results in a crystalline structure, which is significantly different from the structure of bulk undecylenic acid. A phase transition in the wall-adjacent layer of the undecylenic acid nanocrystals was shown to take place. The solid-state phase transition temperatures, as well as the melting point, were shown to be lower for nanocrystals. Topological soliton motion mechanism was suggested to explain the thermal motion of the undecylenic acid molecules in the rotator phase.     

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.     

Etude par Calorimetrie,Diffraction des Rayons X et Diffusion Raman d'une Transition de Phase dans (C4 H4P) Mn (CO)3

Abstract

Heat capacity measurements (95-300K), X-ray diffraction (78-300K) and low frequency Raman spectroscopy (10-350K) have evidenced an order-disorder phase transition in phosphacymantrene, (C₄ H₄P) Mn (CO)₃. This transition has been characterized by a monoclinic ←→ triclinic structural change at about 110 K and by a pretransitional phenomenon. The measured transition enthalpy and entropy are 480 ± 10J.mil^?1 and 4.17 ± 0.08J.K^?1 mol^?1, at 115 K, respectively.

A complete assignment of the observed Raman bands in h₄ and d₄ derivatives is proposed. From the temperature dependence of frequencies, intensities and half-widths of some Raman bands we have discussed the order, the nature and the mechanism of the phase transition: intermolecular interactions appear to be mainly involved in the mechanism and an activation energy roughly equal to 2100 ± 840 J. mol^?1 has been determined.     

New Simple Model of a Liquid Crystal Light Valve

Abstract

A liquid crystal light valve, using a heterojunction indium oxide/silicon of high resistivity (10,000 Ω.cm) and based on the cholesteric-nematic transition is described. The characteristics of this device are determined: optimum voltage to be applied to the cell in order to produce the cholestericnematic phase change, incident light power sensitivity, spectral response, rise and decay times. It has been shown that this light valve has an incident power sensitivity of less than 10 μW.cm^?2 which passes through a maximum for an incident wavelength of 0.8 μm. This valve can be used in the near infrared; rise times of a few tens of ms are obtained.     

Study of melt-grown quasicrystalline samples in the Cd-Yb and Al-Cu-Fe systems

The regimes of preparation of bulk samples of the quasicrystalline phase in the Cd-Yb and Al-Cu-Fe systems have been investigated. A thermodynamically stable quasicrystalline phase Cd_5.7Yb and its approximant Cd₆Yb with a high degree of texture along the cooling axis have been obtained. X-ray diffraction analysis made it possible to reveal changes in the structure and phase composition of bulk samples with variation in the melting temperature and annealing for different methods of sample preparation. It is shown that the presence of a temperature gradient along the furnace axis significantly affects the volume of the quasicrystalline phase. It is established that, with a decrease in the volume of the quasicrystalline phase mixed with the crystalline phase, the character of the temperature dependence of resistivity changes from the semiconductor type to the metallic type and the microhardness decreases according to a linear law.     

Orientational Distribution Function and Order Parameters of Two 4′-Alkoxy-4-Cyanobiphenyls in Mesomorphic Phase

X-ray diffraction studies on samples of 4′-Pentyloxy-4-Cyanobiphenyl and 4′-Octyloxy-4-Cyanobiphenyl over the entire mesomorphic range are reported in this paper. A magnetic field was used to align samples. The orientational distribution functions f(β) have been calculated from the angular distribution of X-ray intensities. Orientational order parameters ( P ₂) and ( P ₄) have been calculated and compared with Maier-Saupe theoretical values. Expressions for the angular part of the pseudopotentials have been obtained from the temperature variation of f(β). The intermolecular distances D have been calculated from the experimental data and it is found that D is significantly smaller for well aligned samples. The apparent molecular length in the nematic phase and the layer thickness in the smectic phase have also been determined and are found to be about 1.4 times larger than the true molecular length in the fully extended form. This is in accordance with the findings from other cyano compounds.     

Heat treatments versus microstructure in a molybdenum-rich borosilicate

A new glass formulation, a calcium and zirconium-enriched alumino-boro-silicate matrix, able to incorporate 12 wt% of molybdenum oxide has been developed in order to trap molybdenum as CaMoO₄, a stable phase in a vitreous medium. Laboratory studies on this matrix have shown the impact of the glass thermal treatment on its microstructure. Thus, four cooling rates and heat treatments presented in this paper were investigated to determine if Ca and Mo totally reacted to give CaMoO₄ and to localize the powellite phase in the different glasses. Using X-ray diffraction and Rietveld refinements, we were able to quantify both crystallized and amorphous CaMoO₄ in all the samples. EDS analyses allowed us to localize it in the glass microstructure. Then coupling together the micrograph analysis and the X-ray diffraction results proved the presence of amorphous powellite and showed its place in the glasses.     

Order Parameters and Distribution Function of 4'-(N-(p-Pentyloxy Carbonyloxy-Benzylidene)Amino) Valerophenone in Smectic Phase from X-ray Diffraction Measurements

Abstract

X-ray diffraction studies of 4'-(N (p-pentyloxycarbonyloxy-benzylidene)amino)valerophenone (PCBAV in short) oriented by a magnetic field is reported here. The compound has a smectic A phase which is identified by X-ray studies and texture studies. Orienta-tional order parameters (p ₂) and (P ₄) have been determined from the calculation of f(β), the orientational distribution function. An approximate expression for the angular part of the potential of the mean field is obtained from the temperature variation of the orientational distribution function. The value of d, the layer thickness, and D, the intermolecular distance, have been calculated. An approximate value for the translational order parameter τ₁ and average value of the root mean square displacement ?z²?½ are given. We could not get an accurate estimate of the translational order parameter due to the inaccuracy in the measurement of the intensity of the inner ring.