Broadband dielectric investigations on a compound consisting of bent-shaped molecules

Dielectric measurements on the antiferroelectric smectic C (SmCP_A) and isotropic (I) phases of a substance formed by bent-shaped molecules were performed in the frequency range from 0.1 Hz to 0.1 GHz. Three absorption ranges, corresponding to a slow collective process, the reorientation of the molecular core around the long axes and the fast dynamics of the terminal groups, were detected in the SmCP_A phase, whereas only two ranges, related to the two last processes, appear in the isotropic state. At the I-SmCP_A phase transition the process of molecular reorientation around the long axes changes stepwise with respect to the absorption band intensity and the relaxation time, while the activation energy remains practically unchanged. The activation energy for the dynamics of the terminal groups increases at the I-SmCP_A transition.     

The binary system composed of a bent-core compound forming a B7 phase and a nematogenic calamitic compound

The isobaric phase diagram for a binary system of liquid crystals is presented. One mixing component is a bent-core mesogen forming a B₇ phase and the other one is a nematogenic calamitic compound. The occurring mesophases have been identified by their optical textures as well as by X-ray investigations. The B₇ phase exists down to about 60 mol% of the bent-core compound A / 40 mol% of the calamitic compound B. Two additional mesophases are induced in the mixed phase region. At medium concentrations (around 50 mol%) an oblique columnar phase appears which shows a similar X-ray pattern to the B₇ phase but an utterly different nucleation on cooling the isotropic liquid and a completely dissimilar texture. At concentrations below 35 mol% A, a further phase is induced which possesses an irregularly modulated layer structure. This phase can be regarded as an intermediate state between the regularly modulated Col_r (B₁) phase and the intercalated B₆ phase. It transforms on cooling into the phase with a regularly modulated structure.     

Structural and calorimetric investigations on nonaqueous liquid crystals and gel phases in the binary system K-stearate/glycerol

The K-stearate/glycerol (KC₁₈/Gl) binary system was studied at mole fractions of stearate of x _KC18 = 0.10, 0.25, 0.30 and 0.50. Small- and wide-angle X-ray diffraction (XRD) measurements were combined with differential scanning calorimetry (DSC) measurements at different temperatures. The investigations were intended to verify the previously published phase diagram and were targeted at the confirmation of the gel-like (G₁) phase and the isotropic (I) phase. The XRD and DSC measurements lead to the conclusion that the G₁ phase as well as the I phase, the existence of which had been proposed from texture observations, do in fact not exist. Consequently, a correction of the preliminary phase diagram is given. This corrected phase diagram reveals the crystalline phase (C) ⇆ gel phase (G) ⇆ hexagonal phase (H_α) ⇆ isotropic, micellar phase phase transitions for low KC₁₈ concentrations of x _KC18 = 0.15–0.3 and the C ⇆ G ⇆ lamellar phase (L_α) phase transitions for concentrations about or higher than x _KC18 = 0.35. The C, G, L_α and H_α phases have been further characterized by structural parameters (characteristic d values) as a function of temperature. The phase transitions C ⇆ G, G ⇆ L_α and G ⇆ H_α correlate with sharp shifts in the d value of the first small-angle reflections. Received: 20 April 1999 Accepted: 28 July 1999     

Structural and calorimetric investigations on nonaqueous liquid crystals and gel phases in the binary system K-behenate/glycerol

Two mixtures of the binary system K-behenate/glycerol, x _KC22 = 0.30 and 0.50 (x = mole fraction), have been investigated as a function of temperature using small- and wide-angle X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The binary phase diagram based on texture observations using polarizing optical microscopy was confirmed. XRD and DSC measurements provided concordant results with respect to the range of the phase regions in the phase diagram. Only differences between the DSC curves for rising and falling temperatures were detected. The recorded XRD and DSC data of the liquid crystals and gel phases observed are also in agreement with previously reported investigations on K-soap/glycerol. The C ⇆ G and G ⇆ L_α phase transitions correlate with a sharp shift in the d value of the first small-angle reflection. The G phase is characterized by a split of the first small-angle reflections. Also, the position and shape of the wide-angle reflections change and the peak intensity is reduced. Received: 5 July 1999 Accepted in revised form: 27 July 1999     

Solid-liquid equilibrium in a binary system with incongruent melting complex compound

Solidus and liquidus equilibrium lines in binary phenol-bisphenol A system were determined with use of a DSC-1B calorimeter. Experimental equilibrium data were correlated by means of liquid phase activity coefficient equations (Redlich-Kister, Van Laar, NRTL) with one constraint based on the condition of solid-liquid equilibrium (Schroeder equation).     

Structural control of mesoporous silica nanoparticles in a binary surfactant system

The grain size and regularity of the hexagonal array of mesoporous silica nanoparticles were investigated in a binary surfactant system composed of cetyltrimethylammonium chloride and triblock copolymer EO106PO60EO106. Structural control was achieved by varying the parameters for the prior hydrolysis of silicon alkoxide under an acidic condition and the subsequent assembly of silicates and surfactants under a basic condition. The formation of the mesoscale architectures was based on the balance between the ordered assembly of anionic silicates and the cationic surfactant through electrostatic interaction and the inhibition of grain growth with a nonionic amphiphilic agent through hydrogen bonds.     

Structural and thermodynamic investigations of an unusual enantiomeric separation: Lipodex E and compound B

Compound B (1,1,3,3,3-pentafluoro-2-fluoromethoxy-1-methoxypropane) can be separated by gas chromatography with an extraordinary chiral separation factor on a column coated with Lipodex E (octakis(3-O-butanoyl-2,6-di-O-n-pentyl)-γ-cyclodextrin). The enantioselectivity is greatly reduced when employing the β-cyclodextrin analogue. To further investigate the background of this unusual separation, the complexation between ‘compound B’ and Lipodex E (octakis(3-O-butanoyl-2,6-di-O-n-pentyl)-γ-cyclodextrin) and heptakis(3-O-butanoyl-2,6-di-O-n-pentyl)-β-cyclodextrin were studied by NMR. Association constants of the interaction of the two enantiomers of compound B with Lipodex E and its β-cyclodextrin analogue were determined by NMR chemical shift titration and showed a large difference corroborating earlier GC results. Heteronuclear NOE measurements proved that inclusion complex formation is taking place with compound B situated inside the cavity of the cyclodextrin moiety. Differences between the inclusion complex structures and their connection to association constants are discussed.     

Structural verification of a tetrahydrotetrazole compound

Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C₂₅H₃₀N₄O₄, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl₃). A tentative reaction pathway for its dissociation based on ¹H NMR spectral evidence is provided.     

Structural,thermal, dielectric and optical behaviour investigations of water-free ZnO/lyotropic liquid crystal nanocolloids

ABSTRACT

Zinc oxide (ZnO) nanoparticles of spherical symmetry (average size of ≈ 20 nm) have been synthesised via a non-aqueous lyotropic liquid crystalline (LLC) templating process. Lyotropic liquid crystalline nanocolloids are prepared via dispersing 0.05, 0.1 and 0.5 wt.% ZnO nanoparticles in non-aqueous lyotropic phase. No structural phase change has been seen with the doping of nanoparticles as stable lamellar phases are observed in all the cases. Stability of the lamellar structure and orientation of the ZnO nanoparticles in the liquid crystalline matrix may be attributed to the interfacial surface charge interactions. A significant increase and pronounced dispersion in dielectric permittivity of the ZnO/LLC nanocolloids could be the result of parallel coupling among guest/host, higher dipole- moment of the ZnO nanoparticles and Maxwell-Wagner polarisation. The variation of relaxation parameters has also been discussed and correlated with the dielectric and structural parameters. ZnO/lyotropic nanocolloids devices exhibit dc conductivity of the order of 10^?5S/m owing to the increase in the number of ions (of the order of 10¹⁹m^?3) in the doped systems. Nanocolloids exhibits, the refractive index of range 1.40 to 1.45 and the wide bandgap of the range 4.1–4.5 eV.     

Thermodynamic investigations of uranium-rich binary and ternary alloys

Uranium–zirconium, uranium niobium, and uranium–zirconium–niobium alloys were synthesized by the arc melting technique and their phase transition temperatures were determined using a high temperature calorimeter. Heat capacities of U–7 wt%Zr, U–7 wt%Nb, U–5 wt%Zr–2 wt%Nb, U–3.5 wt%Nb–3.5 wt%Zr, and U–2 wt%Zr–5 wt%Nb were measured using a differential scanning calorimeter in the temperature range 303–921 K. A set of self-consistent thermodynamic functions such as entropy, enthalpy, and Gibbs energy function data for these binary and ternary alloys were reported for the first time using heat capacity data obtained in this study and required literature data.     

Selected X-ray diffraction and differential scanning calorimetry investigations of the binary system K-palmitate/glycerol

Three mole fractions of the binary system K-palmitate/glycerol (KC₁₆/Gl) x_KC16 = 0.30, 0.37 and 0.50 have been investigated as a function of temperature by small- and wide-angle X-ray diffraction investigations and differential scanning calorimetry (DSC) measurements. The existence of a gel-like region, named G₁ in the preliminary binary phase diagram [4], could not be confirmed. Consequently, a corrected version of the phase diagram of the KC₁₆/Gl system is established. According to this corrected phase diagram at low K-palmitate concentrations, x_KC16 < 0.25, the transitions crystalline phase (C) ⇆ hexagonal phase, chains fluid (H_α) ⇆ isotropic, micellar phase (S) occur with rising temperature. At x_KC16 > 0.25 the transitions C ⇆ gel phase (G) ⇆ lamellar phase, chains fluid (L_α) were observed. X-ray diffraction and DSC measurements provided concordant results. Only differences in the phase transition temperatures from DSC curves obtained at rising and falling temperatures were observed. The phase transitions C ⇆ G, G ⇆ L_α and G ⇆ H_α correlate with a sharp shift in the d value of the first small-angle reflection. The occurrence of the G phase is accompanied by a distinct split of the first small-angle reflections. Simultaneously, the wide-angle reflections change and the peak intensity is reduced. Received: 14 April 1999 Accepted: 28 June 1999     

二元碳氮化合物CN_8的理论研究

采用B3LYP,B3PW91和MP2 3种理论方法优化得到了13种稳定的CN8异构体.对比这些异构体的总能发现分别具有六元杂环结构和平面链状结构的2种异构体是最稳定的结构.进一步计算这2种异构体的生成能和解离掉一个N2的过渡态,发现它们都具有与实验合成的CN12相近的热力学稳定性,并且具有六元杂环结构的异构体展现出更好的动力学稳定性.这些研究结果表明具有六元杂环结构的CN8异构体是可能在实验上合成出来的.     

Structural investigations of alumino-metalloaminocarbene complexes

[Al(NMe₂)₃]₂ combines with Fe(CO)₅ and Mn₂(CO)₁₀ forming bimetallic compounds Fe₂(CO)₈[C(NMe₂)OAl(NMe₂)₂]₂ and Mn₂(CO)₉[C(NMe₂)OAl₂-(NMe₂)₅]. X-ray diffraction analyses reveal the formation of aluminometallocarbene compounds with central connectivities, MC[NMe₂)][OAl(NMe₂)(μ-NMe₂)₂].     

Structural investigations of silicon-rich CVD-SiC

Silicon Carbide (SiC) and Silicon Carbide with free Silicon [SiC(Si)] thin films were prepared by chemical vapor deposition (CVD) using an CH₃SiCl₃-H₂-Ar gas mixture at temperatures of 1173 to 1323 K. The structure of these films were investigated by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The effects of crystallinity, morphology and Si-concentration of the deposits were examinated in some detail.     

Structural investigations of lead-strontium fluoroapatites

Solid solutions in the system Pb_(10−x)Sr_x(PO₄)₆F₂, 0?x?10, were obtained as apatitic phases from aqueous medium. They were investigated by X-ray diffraction, chemical analysis and infrared (IR) spectroscopy. The results of the structural refinements indicated that the substitution of lead by strontium induces a regular decrease of the lattice constant “a” and a preferential strontium distribution in site M(1). A progressive shift of the F⁻ ion position along the apatitic channel was detected and confirmed by IR evidence. The different character of the M-F and M-O interactions was invoked to justify the structural differences observed as a function of composition.     

Nuclear magnetic resonance and dielectric investigations of molecular motions in a glassy crystal: the mixed compound (CN-adm)0.75(Cl-adm)0.25

The dynamic properties of plastic crystalline mixed adamantane's derivatives namely cyanoadamantane (75%) and chloroadamantane (25%) were investigated by dielectric and nuclear magnetic resonance (NMR) spectroscopy, covering a spectral range of 12 decades in the temperature range 110-420 K. Phase transformations were studied and dynamical parameters of the plastic (I), glassy (Ig), and ordered (III) phases were determined and compared with those of pure compounds. The dynamics of the supercooled plastic phase is characterized by an alpha-process exhibiting an Arrhenius behavior which classified the mixed compound as a strong glass former. In the plastic phase, NMR relaxation times were interpreted by using a Frenkel model, which takes into account structural equilibrium positions. This model explains adequately the experimental results by considering two molecular motions. In both the glassy state and plastic phase the motional parameters agree with those of 1-cyanoadamantane. On the contrary, in the ordered phase, the motional parameters related to the uniaxial rotation of chloroadamantane molecules indicate an accelerated motion.     

Calorimetric investigations of hydrogen-bonded liquid crystal binary mixtures

Journal of Thermal Analysis and Calorimetry - Double hydrogen-bonded liquid crystals formed between methyl malonic acid (MM) and p-n-alkyloxy benzoic acids (nBAO) are characterized. Variation in...     

Calorimetric and dielectric investigations of smectic liquid crystals with aerosil

Two strongly polar 4-(4-cyanobenzyloxy)benzylidene 4- n -alkylanilines were synthesized for the first time and mixed with the hydrophilic aerosil A 300. The compounds, showing a rich polymorphism, and the mixtures were investigated by calorimetric and dielectric methods. Phase transitions of first and second order were detected. Neither the phase transition temperatures nor dielectric relaxation times are strongly influenced by addition of aerosil up to 20%.     

Structural investigations on pyrolysed polycarbosilanes

The combination of combustion analysis, IR-spectroscopy and Raman spectroscopy yields information about the chemical state of carbon in polycarbosilanes or silicon carbide. A stable polycarbosilane can be found where carbon is bonded in a network of silicon, carbon and hydrogen. In the temperature range between 700 and 800°C, the polycarbosilane is transformed into an amorphous silicon carbide with a small excess of carbon. During the crystallisation of the amorphous silicon carbide, which takes place at temperatures above 1100°C, glassy carbon is found by Raman-spectroscopy and combustion analysis. Finally after pyrolysis temperatures above 1500°C only silicon carbide exists; this may be caused by the reaction of free carbon with oxygen impurities in the samples.