Synthesis, X-ray diffraction study, and ionic conductivity of new AB2O6 pyrochlores

The oxides A(Ti_0.5Te_1.5)O₆ (A = K, Rb, Cs, Tl), A(Ti_0.5W_1.5)O₆ (A = Rb, Cs, Tl), and Cs(B_0.5W_1.5)O₆ (B = Zr, Hf) have been obtained as polycrystalline powders giving X-ray diffraction patterns characteristic of defect cubic pyrochlores, space group (No. 227), Z = 8. The best discrepancy R factors, from 0.0265 for Rb(Ti_0.5Te_1.5)O₆ to 0.0554 for Cs(Zr_0.5W_1.5)O₆, were obtained for the B cations randomly distributed at 16(d), A ions at one quarter of 32(e), and oxygen atoms at 48(f) positions. A linear relationship is observed between the a unit cell parameters and the ionic radii of the A cations, as well as the average ionic radii of the B atoms. The results of electrical resistivity measurements for A(Ti_0.5Te_1.5)O₆ (A = K, Rb, Cs, Tl) are given.     

Thermal decomposition of novel rare-earth selenites

TG and DTA have been carried out on new anhydrous rare-earth selenites R₂Se_aO_3+2a (a=3.5,4) in order to establish their stability. Decomposition occurs in three steps attributed to successive losses of SeO₂. The first process gives rise to other new group of selenites of composition R₂Se₃O₉, which crystallize in two different forms depending on the rare-earth element. The second process leads to isomorphous compounds R₂SeO₅. The final product of thermal degradation is R₂O₃. All products were characterized by chemical analysis and X-ray powder diffraction methods.     

Excess electrical conductivity in polycrystalline Bi-Ca-Sr-Cu-O compounds and thermodynamic fluctuations of the amplitude of the superconducting order parameter

Measurements of the rounding effects on the electrical resistivity above the superconducting transition in Bi-Ca-Sr-Cu-O polycrystalline compounds are reported, to our knowledge for the first time in this HTSC system. These effects are analyzed in terms of thermodynamic fluctuations of the amplitude of the superconducting order parameter (SCOPF). In the mean-field-like region, the experimental critical exponent seems to be compatible with an order parameter of two components (2d) fluctuating in two dimensions (2D). This contrasts with previous results for A-Ba-Cu-O (A=Y, Ln) and Ln-M-Cu-O (M=Ba, Sr) superconductors, where SCOPF seem to be 2d-3D in all the different dynamic critical regions.     

The series of spinels Co3−sAlsO4 (0 < s < 2): Study of Co2AlO4

Co(III) of Co₃O₄ can be gradually replaced by Al to produce the series of spinels Co_3?sAl_sO₄ (0 < s < 2), S.G. Fd3m (No. 227), Z = 8. For Co₂AlO₄ (s = 1), a = 8.086(1)Å, U = 528.7(2)ų, D_x = 5.25 Mgm^?3, u = 0.264, and 27% of Al in 8(a) positions, R = 0.031. The frequencies of the observed ir absorption bands of Co₂AlO₄ are also presented.     

Preparation and crystal data of the New Pyrochlores Pb2[M1.5Te0.5]O6.5 (M = Ti,Zr, Sn,Hf)

From mixtures of PbO, MO₂ (M = Ti, Zr, Hf), SnO, and TeO₂, four new oxides Pb₂[M_1.5Te_0.5]O_6.5 have been obtained as yellow powders giving X-ray diffraction patterns characteristic of cubic pyrochlores, S.G. Fd3 m (No. 227), Z = 8, and a/Å values from 10.3529(1) (M = Ti) to 10.7406(1) (M = Zr). The best R factors, from 0.0465 (M = Ti) to 0.0242 (M = Hf), were obtained for Pb in 16(c) positions, M and Te (3:1) randomly distributed in 16(d), oxygen atoms in 48(f) and in a half of the 8(a) sites, and x values for the oxygen positional parameter (origin at center, 3 m) from 0.436 (M = Ti) to 0.421 (M = Zr). For the compounds of Ti and Zr the angles of the coordination polyhedra around the metals are reported. For seven-coordinated Pb^II the stereochemical influence of the nonbonded electron pair is shown. Apparent interatomic distances agree with those calculated.     

Crystal Growth and Crystal structure of Gd3Sb5O12: A New Relation between the ccp and the Mn5Si3and Apatite Structures

Red-orange single crystals of Gd₃Sb₅O₁₂ have been grown [hydrothermal conditions, Gd₂O₃ and Sb₂O₃(3:5) in 20% KF solution, 770 K, 1500 bar, 10 days]. The oxide [Mo-Kα, R = 5.4%, I4 3m, with a = 10.8557(4) Å and Z = 4] is isotypic with Pr₃Sb₅O₁₂. Gd and Sb. form a slightly distorted ccp with oxygens occupying 3/4 of the tetrahedral holes, like a fluorite type structure which is also strongly related to the Mn₅Si₃structure type.     

On the Perovskites Ba2LnSbO6 (Ln = Nd,Sm, Eu,Gd, Tb,Dy, Ho,Er, Yb)

Polycrystalline Ba₂LnSbO₆ (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) are cubic, perovskite-type compounds, space group Fm3m (No. 225), Z = 4, with a values from a = 8.544(2) Å for Ba₂NdSbO₆ to a = 8.368(1) Å for Ba₂YbSbO₆. X-ray diffraction data for all the compounds and the results of magnetic measurements for two of them are given.     

Thermal stability of second generation carbosilane dendrimers with peripheral ammonia groups

Spinel nickel zinc ferrite nanowires were successfully prepared in mesoporous silica SBA-15 as a host matrix. The powder was annealed at a range of temperatures (500–900 °C) with heating rate 0.5 °C/min. The required NiZnFe₂O₄ phase was obtained at 700 °C. The specific surface area S_BET data revealed that the surface area of the mesoporous silica after annealing was decreased from 821 to 90 m²/g which indicated that the spinal ferrite fills the channels of mesoporous materials. The one-dimensional spinel nanostructures were characterized by X-ray diffraction, infrared spectroscopy, vibrating sample magnetometer, and transmission electron microscopy before and after a selective removal of the silica template in aqueous solution of NaOH or HF. The presence of SBA-15 lowers the formation temperature of nickel zinc ferrite nanowires compared to the corresponding bulk material. The magnetic properties revealed a high saturation magnetization level (~43 emu/g) for the Ni–Zn nanowires at 900 °C.