Local structure analysis of smoky and colorless topaz using single crystal Al NMR

The angular dependence of the ²⁷Al NMR spectrum was measured for single crystals of smoky and colorless topaz, Al₂SiO₄(F,OH)₂. Smoky topaz was obtained by irradiating high energy neutrons to colorless topaz. The quadrupole coupling constant e²Qq/h and the asymmetry parameter η were obtained from the analysis of the angular dependences of quadrupole splitting of the ²⁷Al NMR spectrum. The local structures around the aluminum atoms in smoky and colorless topaz were discussed from the magnitude and the direction of the electric field gradient. The directions of principal axes of the EFG tensor of ²⁷Al were close to the directions of Al-O and Al-F bonds. The difference in the bond lengths between Al(1)-F(1) and Al(1)-F(2) was found to affect the x and y components of the EFG tensor.     

新型含氧亚甲基和亚胺桥键液晶化合物分子结构与光谱的密度泛函理论研究

采用密度泛函理论方法在B3LYP/6-31G*水平上对6个新型含氧亚甲基和亚胺桥键液晶化合物分子的几何结构进行优化计算,讨论了取代基H,CH3,CH3O,C2H5O,NO2,Cl对分子电荷、前线轨道能量和电子吸收光谱等性质的影响.在此基础上使用含时密度泛函理论方法计算了分子第一激发态的电子垂直跃迁能,得到最大吸收波长λmax.计算表明,取代基的引入导致最大吸收波长红移.     

Structural studies of Cr-doped mullite derived from single-phase precursors

Cr-doped mullites were prepared from single-phase precursors containing up to 9.60 wt% Cr₂O₃ using a sol-gel technique followed by thermal treatment. Particle induced X-ray emission spectroscopy and X-ray powder diffraction were used to characterize the samples. Mullites were orthorhombic, space group Pbam. Cr doping caused the increase of unit-cell parameters. Strongest expansion was noticed along c-axis followed by a and b (Δc/c=0.089, Δa/a=0.061, Δb/b=0.045% per mole Cr₂O₃). A second phase, namely θ-(Al,Cr)₂O₃, was revealed by XRD in the sample containing 9.60 wt% Cr₂O₃. The structure of mullites was refined by the Rietveld method, location of Cr³⁺ was performed by the EPR spectroscopy. At low chromium doping level (Cr₂O₃ content less than ∼5 wt%) Cr³⁺ ions were substituted for Al³⁺ in the AlO₆ octahedra of the mullite structure (M1 site). For higher doping level, Cr³⁺ ions were additionally substituted for Al³⁺ in the AlO₆ octahedra of the second phase [θ-(Al,Cr)₂O₃ at 1400 °C, or α-(Al,Cr)₂O₃ at 1600 °C] which segregated in the system. Substitution of Cr³⁺ for Al³⁺ on M1 site in the mullite structure resulted in increase of average distances in (M1)O₆ octahedron and decrease of average distances in T*O₄ tetrahedron, while average distances in TO₄ tetrahedron stayed almost constant.     

不同方法制备的CO2-3替换磷灰石固溶体晶体化学的FTIR研究

采用不同方法制备了CO2-3替换的磷灰石固溶体,利用FTIR结合XRD对其进行了晶体化学研究,结果表明均相沉淀法制备的碳羟磷灰石(CHAP)属B型替换且替换方式是[CO3·OH]四面体替换[PO4]四面体;固相离子交换法制备的CHAP属A型替换且替换方式是[CO3]三角形配位体替换通道位置的OH-;固相反应法制备的碳氟磷灰石(CFAP)属B型替换,其替换方式是[CO3·F]四面体替换[PO4]四面体;sol-gel法制备的CHAP属AB混合型替换,其Ψ3分裂为Ψ3-1,Ψ3F,Ψ3-4.高斯函数法拟合表明Ψ3F峰是A型替换的Ψ3-2与B型替换的Ψ3-3的叠合.当WCO2-3＜3.34%时,随CO2-3含量增加,A型替换量增大,且当WCO2-3=3.34%时达最大值,当3.34%＜WCO2-3＜7.52%时,随CO2-3含量增加,B型替换量增大,且当WCO2-3= 7.52%时亦到饱和.     

A high-pressure Raman and X-ray diffraction study of the perovskite SrCeO3

A high-pressure structural study of SrCeO₃ has been performed at room temperature by Raman spectroscopy and X-ray diffraction up to 32 and 45 GPa, respectively. A first-order reversible phase transition is observed at about 12 GPa in both techniques. A second weak structural change, taking place between 18 and 25 GPa, can be suspected from Raman data. The increase in the number of Raman bands and diffraction lines is an indication that the symmetry is lowered and the compound does not evolve towards the ideal cubic perovskite structure. A Rietveld analysis of X-ray data was performed for the low-pressure phase and the atomic positions and the cell lattice parameters variations are reported in this paper. The volume compressibility derived from Raman modes (5.6×10⁻¹² Pa⁻¹), involving mainly bond-stretching for each type of polyhedron, is found to be close to the one obtained from volume cell variations measured by X-ray diffraction (7.9×10⁻¹² Pa⁻¹).     

Dynamics of liquid membranes. II: Adaptive finite difference methods

Two domain-adaptive finite difference methods are presented and applied to study the dynamic response of incompressible, inviscid, axisymmetric liquid membranes subject to imposed sinusoidal pressure oscillations. Both finite difference methods map the time-dependent physical domain whose downstream boundary is unknown onto a fixed computational domain. The location of the unknown time-dependent downstream boundary of the physical domain is determined from the continuity equation and results in an integrodifferential equation which is non-linearly coupled with the partial differential equations which govern the conservation of mass and linear momentum and the radius of the liquid membrane. One of the finite difference methods solves the non-conservative form of the governing equations by means of a block implicit iterative method. This method possesses the property that the Jacobian matrix of the convection fluxes has an eigenvalue of algebraic multiplicity equal to four and of geometric multiplicity equal to one. The second finite difference procedure also uses a block implicit iterative method, but the governing equations are written in conservation law form and contain an axial velocity which is the difference between the physical axial velocity and the grid speed. It is shown that these methods yield almost identical results and are more accurate than the non-adaptive techniques presented in Part I. It is also shown that the actual value of the pressure coefficient determined from linear analyses can be exceeded without affecting the stability and convergence of liquid membranes if the liquid membranes are subjected to sinusoidal pressure variations of sufficiently high frequencies.     

The steady state growth rate of a recrystallization front in regions of heterogeneous dislocation density

The paper investigates whether a change from a homogeneous to an inhomogeneous dislocation distribution, assumed to be caused by a slight additional deformation, can lead to an increase of the recrystallization temperature of a deformed metal. In this case, the higher temperature would indicate a more stable deformation structure despite the increase of stored energy. The recrystallization temperature is related to the growth rate. Hence, the steady state velocity of a recrystallization front moving either parallel or vertically to the stripes of a simplified two-dimensional heterogeneous dislocation distribution of parallel sections of higher and lower dislocation densities is calculated. The results show that if a front growths through the high and low density sections in series an overall slower rate despite higher mean dislocation density is, indeed, possible. However, growing in the parallel arrangement always leads to a higher growth rate compared with the homogeneous case of slightly less stored energy. Since in a real structure the faster growth is likely to succeed, the recrystallization temperature observed will be lowered with additional deformation in accordance with experimental experience.     

Improvement of the properties of polyarylate reinforced with liquid crystalline polymers

Blends of polyarylate of bisphenol A, PAr, with two commercial main chain liquid crystalline polymers, Vectra A950 and Vectra B950, are studied. From dynamic viscoelastic measurements it is deduced that both systems (PAr/Vectra A950 and PAr/Vectra B950) are immiscible and scanning electron microscopy (SEM) micrographs show the presence of spherical domains of the liquid crystalline polymer when PAr constitutes the matrix. Extrusion capillary measurements reveal that, under conditions of temperature and shear rate similar to those of processing, the viscosity is reduced to approximately 10% of its value when the content of liquid crystalline polymer is only 20%. This great improvement of the rheological properties is observed in both PAr/Vectra A950 and PAr/Vectra B950 blends. The effect of draw ratio on Young's modulus for different compositions is also analyzed, pointing out the reinforcing action of both liquid crystalline polymers on polyarylate: for instance, 20% of Vectra B950 in the blend gives rise to a 700% increase of the modulus of fibres prepared at a draw ratio of 50. SEM of the extrudates reveals that the spherical domains are elongated at the entrance of the capillary giving rise to a microfibrillar morphology which is related to the excellent rheological and mechanical properties of the blends.     

Use of a long-spacer-side-chain liquid crystalline polysiloxane containing a crown ether as a stationary phase for capillary gas chromatography

A new kind of side chain liquid crystalline polysiloxane containing a crown ether with a longer spacer (PSC-11) has been prepared and coated on a fused silica capillary column. The main chroma-tographic characteristics including efficiency, polarity, and selectivity have been examined. The phase exhibits the retention properties of both liquid crystal and crown ether stationary phases and possesses higher efficiency and better selectivity than PSC-3, which has a shorter spacer between the main polysiloxane chain and liquid crystalline side chain.