Structural characterization of the lithiated iron oxides LixFe3O4 and LixFe2O3 (0<x<2)

Lithium has been inserted into Fe₃O₄ and α-Fe₂O₃ at room temperature both chemically and electrochemically; a compositional range 0<x<2 has been established for both Li_xFe₃O₄ and Li_xFe₂O₃. Powder X-ray-diffraction data of Li_1.5Fe₃O₄ indicate that the [Fe₂]O₄ subarray of the spinel structure remains intact; the A-site Fe³⁺ ions are displaced to empty octahedral positions and the Li⁺ ions in excess of x = 1 are located in tetrahedral sites. Lithiation of α-Fe₂O₃ causes the anion array to transform from hexagonal to cubic close packing; in this case the Li⁺ ions are distributed over both 16c and 16d octahedral sites of the cubic space group Fd3m.     

Medium-entropy(Me,Ti)0.1(Zr,Hf,Ce)0.9O2(Me = Y and Ta): Promising thermal barrier materials for high-temperature thermal radiation shielding and CMAS blocking

With continuous enhancement of gas-turbine inlet temperature and rapid increase of radiant heat transfer,thermal barrier coating(TBC) materials with a combination of low thermal conductivity and good high-temperature thermal radiation shielding performance play vital roles in ensuring the durability of metallic blades.However,yttria-stabilized zirconia(YSZ),as the state-of-the-art TBC and current industry standard,is unable to meet such demands since it is almost translucent to high-temperature ...     

Crystal structure and ionic conductivity of ruthenium diphosphate ARu2(P2O7)2, A=Li, Na, and Ag, with a tunnel structure

Crystal structure and ionic conductivity of ruthenium diphosphates, ARu₂(P₂O₇)₂ A=Li, Na, and Ag, were investigated. The structure of the Ag compound was determined by single crystal X-ray diffraction techniques. It crystallized in the triclinic space group P−1 with a=4.759(2) Å, b=6.843(2) Å, c=8.063(1) Å, α=90.44(2)°, β=92.80(2)°, γ=104.88(2)°, V=253.4(1) Å³. The host structure of it was composed of RuO₆ and P₂O₇ groups and formed tunnels running along the a-axis, in which Ag⁺ ions were situated. The ionic conductivities have been measured on pellets of the polycrystalline powders. The Li and Ag compounds showed the conductivities of 1.0×10⁻⁴ and 3.5×10⁻⁵ S cm⁻¹ at 150 °C, respectively. Magnetic susceptibility measurement of the Ag compound showed that it did not obey the Curie-Weiss law and the effective magnetic moment decreased as temperature decreased due to the large spin-orbital coupling effect of Ru⁴⁺ ions.     

Synthesis and study of compounds A 2I (UO2)2Si5O13 · 3H2O (AI = Na, K)

Sodium and potassium diuranyl pentasilicates were prepared by precipitation from a solution followed by hydrothermal treatment. The structure, properties, and thermal behavior of these compounds were studied by X-ray diffraction, IR spectroscopy, and thermal analysis. Original Russian Text ? N.G. Chernorukov, A.V. Knyazev, A.A. Sazonov, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 2, pp. 114–115.     

Crystal Structure of Tl2[(UO2)2(MoO4)3] and Crystal Chemistry of the Compounds M2[(UO2)2(MoO4)3] (M = Tl, Rb, Cs)

A new compound, Tl₂[(UO₂)₂(MoO₄)₃], was prepared by a solid-phase reaction. The compound crystallizes in a rhombic system, space group Pna2₁, a = 20.1296(9), b = 8.2811(4), c = 9.7045(4), V = 1617.69(13) ų, Z = 4. The crystal structrue was solved by the direct method and refined to R ₁ = 0. 04 for 4884 unique reflections. The structural motif is a framework consisting of UO₇ pentagonal bipyramids and MoO₄ tetrahedra. The Tl coordination polyhedra are irregular, with seven and eight vertices. Large channels of the size 6 × 10.8 Å, occupied by Tl⁺ cations, are arranged parallel to the [001] direction. The compound is isostructural to the previously described α-Cs₂(UO₂)₂(MoO₄)₃ and Rb₂(UO₂)₂ (MoO₄)₃. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 408–411. Original Russian Text Copyright ? 2005 by Nazarchuk, Krivovichev, Burns.     

Electrical conductivity of polycrystalline Fe2(MoO4)3

Measurements of the electrical conductivity of polycrystalline Fe₂ (MoO₄)₃ in the temperature range 370 to 900 K and in the oxygen partial pressure region 10^?4 to 1 atm are presented. Fe₂(MoO₄)₃ is found to be a semiconductor. Differing conduction mechanisms operate, depending on the crystallographic form of Fe₂(MoO₄)₃ and the oxygen partial pressure, and their nature is discussed.     

Crystal Structure of (H3O)6[(UO2)5(SeO4)8(H2O)5](H2O)5

Crystals of (H₃O)₆[(UO₂)₅(SeO₄)₈(H₂O)₅](H₂O)₅ were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 13.835(2), b = 13.4374(16), c = 14.310(3) Å, β = 108.004(14)°, V = 2530.1(7) Å ³] was solved by the direct method and refined to R ₁ = 0.090 for 4409 reflections with |F _hkl ≥ 4σ|F _hkl |. The structure is based on [(UO₂)₅(SeO₄)₈(H₂O)₅]⁶⁻ layers arranged parallel to the (101) plane; these layers have a unique topological structure. The U(1)O₆(H₂O) and U(3)O₆(H₂O) linked through selenate groups form chains running along [ [`1]\bar 1 01] direction. The chains are combined in layers by U(2)O₆(H₂O) bipyramids. The layers are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups located between the layers.     

Crystal Structure of (H3O)2[(UO2)2(SeO4)3(H2O)2](H2O)3.5

Crystals of (H₃O)₂[(UO₂)₂(SeO₄)₃(H₂O)₂](H₂O)_3.5 were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 11.9402(11), b = 13.6452(14), c = 13.7271(12) Å, β = 109.436(7)°, V = 2109.1(3) ų] was solved by the direct method and refined to R ₁ = 0. 048 (wR ₂ = 0. 082) for 3677 reflections with |F _hkl |F _hkl |. The structure consists of [(UO₂)₂(SeO₄)₃(H₂O)₂]₂₋ layers arranged parallel to the (010) plane. The layers are formed by uranium and selenium coordination polyhedra sharing common vertices and are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups arranged between the layers. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 412–414. Original Russian Text Copyright ? 2005 by Krivovichev, Kahlenberg.     

The luminescence of doped and undoped BaLn2(MoO4)4 (Ln = La,Gd)

The luminescence of nominally pure BaLn₂(MoO₄)₄ (Ln = La,Gd) is reported. Below 300 K molybdate emission is observed. The following activators were investigated: Eu³⁺, Tb³⁺, Pb²⁺ and Bi³⁺. The two lanthanide ions show their characteristic emission, the two s² configuration ions give an emission in which the host-lattice group as well as the activator is involved. The luminescence properties of these compositions are discussed and compared with those of related materials.     

Luminescent properties of glassy and crystallized (Li2B4O7 + xB2O3)0.999(MnO2)0.001 (x = 0–16.67 mol %) materials

We have studied the thermoluminescence (TL) and roentgenoluminescence (RL) of glassy and crystallized (Li₂B₄O₇)_0.999(MnO₂)_0.001-(Li₄B₁₀O₁₇)_0.999(MnO₂)_0.001 samples. The results demonstrate that annealing influences the relative TL and RL intensities in the samples owing to crystallization processes. The TL and RL intensities of the crystalline materials are several times higher than those of the thermoluminescent material (Li₂B₄O₇)_0.999(MnO₂)_0.001 and have a maximum at B₂O₃ excesses of 7–11 mol %. Original Russian Text ? V.M. Holovey, V.I. Lyamayev, A.M. Solomon, N.N. Birov, P.P. Puga, V.T. Maslyuk, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 7, pp. 841–845.     

Crystal structure and cation transport properties of the ortho - diphosphates Na7(MP2O7)4PO4 (M = Al,Cr, Fe)

The isotypic ortho-diphosphates Na₇(MP₂O₇)₄PO₄ (M = Al, Cr, Fe) have been synthesized. They are tetragonal, space group P4&#x0304;2₁c. The structure of the iron member has been solved and refined to a final R = 0.037 for 577 independent reflections. It consists of (FeP₂O₇)₄PO₄ units interconnected so as to form a 3D framework into which the sodium ions are inserted. The units are made of a PO₄ tetrahedron linked to four FeO₆ octahedra; each octahedron is connected to a P₂O₇ group by two oxygens. Ion exchange experiments and conductivity measurements give evidence of some mobility of the sodium ions at high temperature. However, the σ-values ($\text{～ 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$ at 300°C) are relatively low. The narrowness of the windows between the sodium sites as well as the presence of an oxygen atom linked to only one polyhedron of the framework are unfavourable features to fast cation transport.     

Preparation of (NH4)Zr2(PO4)3 and HZr2(PO4)3

(NH₄)Zr₂(PO₄)₃ has been prepared, hydrothermally, from α-zirconium phosphate in three different ways; (1) from amine intercalates at 300°C, (2) from mixtures of ZrOCl₂·8H₂O in excess (NH₄)H₂PO₄ and (3) reaction of NH₄Cl with Zr(NaPO₄)₂. Ammonium dizirconium triphosphate is rhombohedral with a = 8.676(1) and $\text{c}\text{= 24.288(5)}\text{A}\text{?}$. It decomposed on heating to HZr₂(PO₄)₃. Below 600°C a complex, as yet unindexed, X-ray pattern was obtained. A very similar X-ray pattern was obtained by washing LiTi_0.1Zr_1.9(PO₄)₃ with 0.3N HCl. Heating this phase or NH₄Zr₂(PO₄)₃, above 600°C resulted in the appearance of a rhombohedral phase of HZr₂(PO₄)₃ with cell dimensions a = 8.803(5) and $\text{c}\text{= 23.23(1)}\text{A}\text{?}$. The protons were not completely removed until about 1150°C. Decomposition of (NH₄)Zr₂(PO₄)₃ at 450°C yielded an acidic gas whereas at 700°C NH₃ was evolved. A possible explanation for this behavior is presented.     

Structure cristalline de Mn0, 4Er4, 6S7

The crystal structure of Mn₀, ₄Er₄, ₆S₇ ($\text{a}\text{= 12,573 (4)}\text{A}\text{?}$, $\text{b}\text{= 11,390 (4)}\text{A}\text{?}$, $\text{c}\text{= 3,777 (4)}\text{A}\text{?}$, γ = 105,45°, space group B2/m, Z = 2) has been refined by a least square method to a final R = 0,045, with 1431 independant reflections. The octahedral positions are occupied either by Er and Mn atoms or by Er atoms only and the prismatic sites by Er atoms.     

Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.     

Crystal structures of CdTi2O4(OH)2 and LaTiSbO6

The crystal structures of two PbSb₂O₆-type compounds containing titanium, CdTi₂O₄(OH)₂ and LaTiSbO₆ were refined by X-ray powder diffraction data. For both compounds structure refinements with the space group were successful and the R-factors were R_WP = 6.46% and R_P = 4.90% for CdTi₂O₄(OH)₂ and R_WP = 9.55% and R_P = 7.17% for LaTiSbO₆. These crystal structures were the same as that of the typical PbSb₂O₆-type compound in spite of the existence of protons in the interlayer or two different metal ions in the layer.     

Crystal structure of complexes of Np(VI) and Pu(VI) perchlorates with triphenylphosphine oxide, [NpO2(OP(C6H5)3)4](ClO4)2 and [PuO2(OP(C6H5)3)4](ClO4)2

Single crystals of [NpO₂(TPPO)₄](ClO₄)₂ and [PuO₂(TPPO)₄](ClO₄)₂ isostructural to the complex [UO₂(TPPO)₄](ClO₄)₂ [TPPO = OP(C₆H₅)₃] studied previously were prepared, and the structures of these compounds were determined. The coordination polyhedron of these compounds is a tetragonal bipyramid. The geometric characteristics of the tetragonal bipyramids in the compounds are practically the same despite the actinide contraction of the central atoms, whereas the unit cell volume decreases in the series U-Np-Pu. The equality of the volumes of the coordination polyhedra of the U, Np, and Pu atoms is attributed to the influence of TPPO containing phenyl radicals with negative effective charge. Original Russian Text ? I.A. Charushnikova, N.N. Krot, Z.A. Starikova, I.N. Polyakova, 2007, published in Radiokhimiya, 2007, Vol. 49, No. 5, pp. 407–411.     

Synthesis and structural characterization of (Bi2O3)1?x (Y2O3)x and (Bi2O3)1?x (Gd2O3)x solid solutions

Solid solution series, (Bi₂O₃)_1−x (Y₂O₃)_x and (Bi₂O₃)_1−x (Gd₂O₃)_x, forx = 0.10, 0.20, 0.30 and 0.40 were synthesized by standard ceramic technique. The structural phase characterization was carried out using X-ray powder diffraction technique. It was found that the solid solution containing 20–40 mole% of Y₂O₃ had face-centred cubic structure. All samples of the solid solution series, (Bi₂O₃)_1−x (Gd₂O₃)_x, had rhombohedral single phase in the concentration range 0.10 ≤x ≤ 0.40. Lattice parameters offcc phase of Y₂O₃ doped samples were calculated from the X-ray diffraction data. The lattice constant ‘a’ gradually decreases with increasing content of dopant concentration (x) for the Y₂O₃ doped system and obeys Vegard’s rule. The unit cell parameters for the (Bi₂O₃)_1−x (Gd₂O₃)_x doped samples showing rhombohedral phase were obtained on hexagonal setting.     

苯胺-SrTi(C2O4)2颗粒制备及其电流变性能

用沉淀法制备了苯胺-草酸氧钛锶（SrTi（C₂O₄）₂）颗粒。FTIR分析表明,苯胺已引入到SrTi（C₂O₄）₂颗粒的表面;XRD分析表明,苯胺-SrTi（C₂O₄）₂颗粒为含少量结晶的无定形态。采用SEM观察颗粒的形貌,结果表明,随反应体系中苯胺与钛原子物质的量比n_aniline/n_Ti的增大,苯胺-SrTi（C₂O₄）₂颗粒由近似球状（n_aniline/n_Ti =0）变为多面体状（n_aniline/n_Ti =2）,而后变为棒状与团簇状颗粒的混合体系（n_aniline/n_Ti =3）。以苯胺-SrTi（C₂O₄）₂颗粒为分散相制备颗粒质量分数为66.7%电流变液,电流变性能测试结果表明,在n_aniline/n_Ti =2时,电流变液具有较高的剪切应力和剪切屈服强度、较大的漏电流密度。苯胺在颗粒制备过程中起控制颗粒形貌的作用,在电流变液体系中起极性分子的作用,其对苯胺-SrTi（C₂O₄）₂电流变液性能的影响是两种效应综合作用的结果。     

Synthesis of Nanotubular Mg3Si2O5(OH)4-Ni3Si2O5(OH)4 Silicates at Elevated Temperatures and Pressures

Mg₃Si₂O₅(OH)₄-Ni₃Si₂O₅(OH)₄ nanotubes with the chrysotile structure and MgO : NiO molar ratios of 1 : 2 and 2 : 1 are synthesized by hydrothermal reactions at temperatures from 250 to 450°C and pressures from 30 to 100 MPa. The reaction path and kinetics, as well as the dimensions and morphology of the resulting nanotubes, are shown to depend on the nature of the starting reagents, chemical composition of the reaction system, and hydrothermal synthesis conditions. At higher nickel concentrations in the hydrous silicates, nanotube formation requires higher temperatures, longer hydrothermal treatment times, and higher NaOH concentrations in the reaction system.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 849–855.Original Russian Text Copyright © 2005 by Korytkova, Maslov, Pivovarova, Polegotchenkova, Povinich, Gusarov.