A new anatase-type phase in the system Mg-Ta-O-N

Magnesium doped tantalum oxynitrides were prepared by ammonolysis of amorphous mixed oxides. An orange colored anatase-type phase with the composition Mg_0.05Ta_0.95O_1.15N_0.85 was found. It is metastable and undergoes a phase transformation to a baddeleyite-type phase between 900 and 1000 °C. X-ray diffraction measurements indicate spacegroup I4₁/amd with lattice parameters and . A possible anion ordering was examined by theoretical methods and neutron diffraction experiments. In addition, anosovite-type (Ti₃O₅) phases Mg_xTa_3−xO_3xN_5−3x; 0?x?0.3 were obtained. The electronic spectra of all phases were investigated by UV/vis spectroscopy.     

Luminescent and structural properties of the series Ba6−xEuxTi2+xTa8−xO30 and Ba4−yKyEu2Ti4−yTa6+yO30

The series Ba_6−xEu_xTi_2+xTa_8−xO₃₀ and Ba_4−yK_yEu₂Ti_4−yTa_6+yO₃₀ have been synthesized at 1400°C in air. They exhibit efficient excitation at about 400 nm and typical emission of Eu³⁺ at about 580-620 nm, form solid solutions within 0.0?x?2.0 and 0?y?4 respectively, and crystallized in P4/mbm at room temperature with Eu atoms occupied at centrosymmetric site (0, 0, 0). Their conductivity is very low (2.8×10⁻⁶ Ω⁻¹ cm⁻¹ at 740°C for Ba₆Ti₂Ta₈O₃₀).     

Luminescence in some tantalate host lattices

The luminescence of the following systems are reported: ScTa_1−xNb_xO₄, Li₃Ta_1−xNb_xO₄, CaTa_2−2xNb_2xO₆ and Mg₄Ta_2−2xNb_2xO₉. The dependence of the luminescence properties on x becomes more pronounced if the distance between the pentavalent ions becomes shorter. In these systems the NbO₆ group gives an efficient blue emission at 300°K. The compound Mg₄Ta₂O₉ gives an efficient ultraviolet emission at 300°K. At 77°K both Mg₄Nb₂O₉ and Mg₄Ta₂O₉ show in addition a weaker emission peaking at wavelengths longer than the wavelength of the room temperature emission. This low-temperature emission can be excited by radiation with wavelengths longer than that of the absorption edge. The Mn²⁺ ion in Mg₄Ta₂O₉Mn acts as an efficient activator with a deep-red emission.     

A high-temperature structure for Ta2O5 with modulations by TiO2 substitution

Solid solutions in the series (1−x)Ta₂O₅−xTiO₂ with x=0.0-0.1 were prepared by high-temperature ceramic processing methods, and the crystal structure was determined at room temperature by transmission electron microscopy, electron diffraction and high-resolution lattice imaging. A structural model is proposed for the oxygen-deficient tantalum oxide (Ta₂O₅) phase with high TiO₂ doping level (x=0.08). The model is based on edge sharing of an oxygen octahedron-hexagonal bi-pyramid-octahedron molecular building block unit that repeats four times per unit cell. Electron diffraction reveals a monoclinic distortion from a pseudo-tetragonal model structure that is modulated primarily along 〈110〉. The modulation length varies with increasing TiO₂ content. Furthermore, by quantitative HREM analysis and matching of lattice images by simulation, it is shown that the modulation is associated with small ionic displacements in specific lattice planes that coincide with Ta ions in the model structure coordinated by oxygen hexagonal bi-pyramids. Based on this evidence, it is suggested that the modulation comes from a replacement of Ta with Ti ions, and the loss of inversion symmetry in the modulated structure is related to the dielectric properties of the material.     

Synthesis of new molybdenum-tungsten, vanadium-tungsten and vanadium-molybdenum-tungsten oxynitrides from freeze-dried precursors

Interstitial molybdenum-tungsten, vanadium-tungsten and vanadium-molybdenum-tungsten oxynitrides in the solid solution series Mo_1−zW_z(O_xN_y) and V_1−zW_z(O_xN_y) (z=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1), and V_1−u−zMo_uW_z(O_xN_y) (u, z=0.2, 0.33, 0.4, 0.6; u+z<1), have been obtained by ammonolysis of precursors resulting from the freeze-drying of aqueous solutions of the metal salts (NH₄VO₃, (NH₄)₆Mo₇O₂₄·4H₂O and (NH₄)₆W₁₂O₃₉·18H₂O). A study of the influence of the preparative variables on the outcomes of this procedure is presented. Compounds in the Mo_1−zW_z(O_xN_y) series are prepared as single phases by ammonolysis of the respective freeze-dried precursors (during 2 h) at different temperatures between 973 and 1023 K, optimised for each composition, followed by slow cooling of the samples (except for the Mo-only containing phase, in which fast cooling has been used). Compounds in the V_1−zW_z(O_xN_y) and V_1−u−zMo_uW_z(O_xN_y) series are prepared as single phases by ammonolysis (during 2 h) of crystalline precursors (as resulting from thermal treatment in air at 873 K, during 12 h, of the freeze-dried precursors) at 1073 K, followed by slow cooling of the samples. All the compounds in these series have the rock-salt crystal structure, in which the metal atoms are in an fcc arrangement, with non-metal atoms occupying octahedral interstitial positions. The materials have been characterized by X-ray powder diffraction, elemental analysis, scanning electron microscopy and magnetic measurements.     

Synthesis of nanopowders of pentoxides Ta2y Nb2(1−y)O5

The processes of production of high purity nanopowders of niobium and tantalum pentoxide Ta_2y Nb_2(1–y)O₅ with a low content of fluorine and Nb₂O₅ in low-temperature polymorph were studied. Ceramic samples were prepared from a charge of solid solutions LiTa _y Nb_1–y O₃ and Li _x Na_1–x Ta _y Nb_1–y O₃ synthesized using coprecipitated pentoxide Ta_2y Nb_2(1–y)O₅. Therewith for solid solutions LixNa_1–x Ta _y Nb_1–y O₃ significantly larger values of high dielectric constant and ionic conductivity were achieved compared to the solid solutions obtained by using a mechanical mixture of Ta₂O₅ and Nb₂O₅. This converts solid solutions LixNa_1–x Ta _y Nb_1–y O₃ from acoustoelectronic and piezoelectric type of materials into the capacitor and ion-conductive type of solid materials.     

Phase equilibria and crystal structure of the complex oxides in the Ln-Ba-Co-O (Ln=Nd, Sm) systems

The phase equilibria in the Ln-Ba-Co-O (Ln=Nd, Sm) systems were systematically studied at 1100 °C in air. The homogeneity ranges and crystal structure of the solid solutions: Ln_2−xBa_xO_3−δ (0<x≤0.1 for Ln=Nd and 0<x≤0.3 for Ln=Sm), Nd_3−yBa_yCo₂O₇ (0.70≤y≤0.80), BaCo_1−zSm_zO_3−δ (0.1≤z≤0.2) were determined by X-ray diffraction of quenched samples. The values of oxygen content (5+δ) for slowly cooled LnBaCo₂O_5+δ (Ln=Nd, Sm) samples were estimated as 5.73 for Ln=Nd, and 5.60 for Ln=Sm. The unit cell parameters were refined using Rietveld full-profile analysis. It was shown that NdBaCo₂O_5.73 possesses tetragonal structure and SmBaCo₂O_5.60 - orthorhombic structure. The projections of isothermal-isobaric phase diagrams for the Ln-Ba-Co-O (Ln=Nd, Sm) systems to the compositional triangle of metallic components were presented.     

Sur de nouveaux germanates et silicates de type bénitoïte

Five new “benitoïte” type germanates: ATaGe₃O₉ (A = K, Rb, Tl), RbNbGe₃O₉, and the silicate BaSnSi₃O₉ were synthesized. Solid solutions A(Ta_1−xNb_x) Ge₃O₉, ATa(Ge_3−ySi_y)O₉ (A = K, Rb, Tl) and BaSn(Ge_3−ySi_y)O₉ were also studied. Positions of atoms in the hexagonal cell were determined from intensity of X-ray powder diffraction patterns.     

Relationship between interlayer hydration and photocatalytic water splitting of A′1−xNaxCa2Ta3O10·nH2O (A′=K and Li)

Partial replacement of alkaline metals in anhydrous KCa₂Ta₃O₁₀ and LiCa₂Ta₃O₁₀ was studied to control interlayer hydration and photocatalytic activity for water splitting under UV irradiation. A′_1−xNa_xCa₂Ta₃O₁₀·nH₂O (A′=K and Li) samples were synthesized by ion exchange of CsCa₂Ta₃O₁₀ in mixed molten nitrates at 400 °C. In K_1−xNa_xCa₂Ta₃O₁₀·nH₂O, two phases with the orthorhombic (C222) and tetragonal (I4/mmm) structures were formed at x?0.7 and x?0.5, respectively. Upon replacement by Na⁺ having a larger enthalpy of hydration (ΔH_h⁰), the interlayer hydration occurred at x?0.3 and the hydration number (n) was increased monotonically with an increase of x. Li_1−xNa_xCa₂Ta₃O₁₀·nH₂O showed a similar hydration behavior, but the phase was changed from I4/mmm (x<0.5, n∼0) via P4/mmm (x∼0.5, n∼1) to I4/mmm (x∼1.0, n∼2). The photocatalytic activities of these systems after loading 0.5 wt% Ni were quite different each other. K_1−xNa_xCa₂Ta₃O₁₀·nH₂O exhibited the activity increasing in consistent with n, whereas Li_1−xNa_xCa₂Ta₃O₁₀·nH₂O exhibited the activity maximum at x=0.77, where the rates of H₂/O₂ evolution were nearly doubled compared with those for end-member compositions (x=0 and 1).     

Divergent effects of static disorder and hole doping in geometrically frustrated β-CaCr2O4

The gallium substituted and calcium deficient variants of geometrically frustrated β-CaCr₂O₄, β-CaCr_2-2xGa_2xO₄ (0.02≤x≤0.25) and β-Ca_1−yCr₂O₄ (0.075≤y≤0.15), have been investigated by X-ray powder diffraction, magnetization and specific heat measurements. This allows for a direct comparison of the effects, in a geometrically frustrated magnet, of the static disorder that arises from non-magnetic substitution and the dynamic disorder that arises from hole doping. In both cases, disturbing the Cr³⁺ lattice results in a reduction in the degree of magnetic frustration. On substitution of Ga, which introduces disorder without creating holes, a gradual release of spins from ordered antiferromagnetic states is observed. In contrast, in the calcium-deficient compounds the introduction of holes induces static ferrimagnetic ordering and much stronger perturbations of the β-CaCr₂O₄ host.     

Structural characterization and electrical properties of NiNb2−xTaxO6 (0≤x≤2) and some Ti-substituted derivatives

A structural and electrical characterization of the system NiNb_2−xTa_xO₆ (0≤x≤2) is presented. For x≤0.25 materials with the columbite-type structure typical of NiNb₂O₆ have been obtained whereas for x≥1 tri-rutile-like oxides were obtained. The electrical properties are similar in both cases; they are semiconducting with very low electrical conductivity and very high activation energy, though slight differences were found as a function of Ta content. Improvement of conductivity by reducing the stoichiometric materials could not be achieved due to decomposition. In this connection, partial substitution of Nb or Ta by Ti has been carried out in order to create oxygen vacancies. Tantalum was partially replaced by Ti to a significant extent in the tri-rutile structure inducing a slight increasing of conductivity. However, for the columbite case neither Nb nor Ta could be partially replaced. This behavior is quite different from that reported for other similar columbites such as MnNb₂O_6−δ, which exhibits high electrical conductivity upon substitution of niobium by titanium.     

Different [Bi12O14]n Columnar Structural Types in the Bi-Mo-Cr-O System: Synthesis, Structure, and Electrical Properties of the Solid Solution Bi26Mo10−xCrxO69

In order to search for new ionic conductor materials exhibiting a columnar [Bi₁₂O₁₄] structural type, the syntheses of the solid solutions Bi₂Mo_1−xCr_xO₆ and Bi₂₆Mo_10−xCr_xO₆₉ have been undertaken. Single phases were obtained for the last composition with 0≤x≤5 homogeneity range. Moreover, a new oxide with Bi₆Cr₂O₁₅ composition has been obtained from the limit nominal stoichiometries Bi₆CrO₆ and Bi₂₆Cr₁₀O₆₉. X-ray powder diffraction studies have shown that this oxide crystallizes in the orthorhombic system, space group Ccc2 or Cccm, with unit-cell parameters a=19.8986(9) Å, b=12.2756(6) Å, c=5.8868(3) Å, and V=1437.96 ų. Impedance spectroscopy measurements carried out on the representative Bi₂₆Mo₈Cr₂O₆₉ phase, showed that this material is a good oxygen ion conductor, in fact the best one belongs to the columnar structural type, with a conductivity as high as 1.7×10⁻³Scm⁻¹ at 425°C.     

p(O2)-stability of LaFe1−xNixO3−δ solid solutions at 1100 °C

LaFe_1−xNi_xO_3−δ (x=0.1−1.0) perovskites were synthesized via citrate route. The p(O₂)-stability of the perovskite phases LaFe_1−xNi_xO_3−δ has been evaluated at 1100 °C based on the results of XRD analysis of powder samples annealed at various p(O₂) and quenched to room temperature. The isothermal LaFeO_3−δ-“LaNiO_3−δ” cross-section of the phase diagram of the La-Fe-Ni-O system has been proposed in the range of oxygen partial pressure −15<log p(O₂)/atm≤0.68. The unit cell parameters of orthorhombic perovskites O-LaFe_1−xNi_xO_3−δ increase with decrease in p(O₂) at fixed composition x. This behavior is explained on the basis of size factor. The decomposition temperatures of rhombohedral phases R-LaFe_1−xNi_xO_3−δ for x=0.7, 0.8, 0.9 and 1.0 in air were determined as 1137, 1086, 1060 and 995 °C, respectively.     

Energetics of magnesium, strontium, and barium doped lanthanum gallate perovskites

LaGaO₃ perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa_1−yMg_yO_3−δ (LGM), La_1−xSr_xGa_1−yMg_yO_3−δ (LSGM), and La_1−xBa_xGa_1−yMg_yO_3−δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of V_O^·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling.     

Crystal chemistry of the (Ta6Si4O26)6− and (Ta14Si4O47)8− frameworks

The range of chemical flexibilities of the hexagonal frameworks (Ta₆Si₄O₂₆)^6? and (Ta₁₄Si₄O₄₇)^8? have been partially explored. This has been done with high-temperature preparations as in general ionic mobilities in these frameworks are too low to permit low-temperature ion exchange. Ionic site potential calculations indicate that preferential site-occupancy factors as well as geometric constraints are responsible for the absence of ionic motion. New phases K_6?xNa_xTa₆Si₄O₂₆ (x ? 4), K_8?xNa_xTa₁₄Si₄O₄₇ (x ? 5), and impure Ba_3?xNa_2xTa₆Si₄O₂₆ have been prepared. Introduction of up to 2 moles of Li⁺ and 1 mole of Mg²⁺ ions per formula unit into sites of the framework not normally occupied has been demonstrated as well as the possibility of partially substituting Zr⁴⁺ for Ta⁵⁺ ions. Substitutions designed to introduce large tunnel vacancies in the presence of only monovalent K⁺ or Na⁺ ions (P for Si, W for Ta and F for O) generally proved unsuccessful. Competitive phases also frustrated attempts to substitute either the larger Rb⁺ or the smaller Li⁺ ions into the large-tunnel sites. A large area of solid solution was discovered in the BaONa₂OTa₂O₅ phase diagram; it has a (TaO₃)-framework with the structure of tetragonal potassium tungsten bronze.     

Synthesis and structural analysis of Bi2−ySryIr2O7, a new pyrochlore solid solution

This paper presents a study of the synthesis and structural properties of the new pyrochlore-type Bi_2−ySr_yIr₂O₇ series. Ten compositions with 0.0≤y≤0.9 were prepared by solid-state reaction with thermal treatments at 873, 1073 and 1323 K under atmospheric pressure conditions. Structural refinements from X-ray powder diffraction data by the Rietveld method show that all compounds of the Bi_2−ySr_yIr₂O₇ solid solution crystallize in a α-pyrochlore structure. The main structural difference when bismuth is substituted by strontium concerns the x position of the O1 (x, ?, ?). This substitution significantly increases the Bi/Sr-O1 distance and diminishes the Ir-O1 distance; this implies that the Ir-O1-Ir bond angle increases. With the Sr substitution, the IrO₆ local configuration goes from a flattened trigonal antiprism, y<0.5, to an elongated one, y>0.5, passing through an octahedral array, y∼0.5. The electrical consequences of these structural changes observed in this system are qualitatively explained with electronic structure calculations, this behavior agrees very well with those observed in other pyrochlore systems A₂M₂O₇ (A=rare earth cations or Tl⁺, Pb²⁺, or Bi³⁺, and M=Ru or Ir).     

Structural and physical properties evolution of BaIr1−xMnxO3 solid solutions synthesized by high-pressure sintering

The BaIr_1−xMn_xO₃ (0.0≤x≤1.0) solid solutions were synthesized by using the solid-state chemical method and high pressure sintering in the pressure range 0-5 GPa. According to the pressure-composition “phase diagram” at 1000 °C, the 9M BaIr_1−xMn_xO₃ transforms to the 6M form at 5 GPa and x≤1/6. In the x range 0.5-1.0, it transforms to the 9R form in a large pressure range. For the 9M BaIrO₃, the Mn ions substitution for Ir ions enhances the semiconducting property, and reduces the weak ferromagnetism. When x is larger than 1/3, the 9M/9R BaIr_1−xMn_xO₃ behave spin-glass-like state at low temperature, with the glass transition temperature T_g about 60 K. For the 6M BaIrO₃, the Mn ions doping results in that it transforms to insulator and spin-glass-like magnetism from the initial paramagnetic metal.     

Structural Characterization of the Complex Perovskites Ba1−xLaxTi1−xCrxO3

The series Ba_1−xLa_xTi_1−xCr_xO₃ (0≤x≤1) was synthesized at 1400°C for about 60 h. Their structure was carefully analyzed by the use of powder X-ray diffraction and Rietveld analysis software GSAS (General Structure Analysis System). Four solid solutions are found in this series: tetragonal solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0≤x≤0.029), cubic solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.0365≤x≤0.600), rhombohedral solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.700≤x≤0.873), and orthorhombic solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.956≤x≤1). There are corresponding two-phase regions between the adjacent two solid solutions. The detailed lattice parameters are presented. The relationship between the lattice parameters and the composition of the solid solutions is developed.     

Evolution of structural distortions in solid solutions between BiMnO3 and BiScO3

Crystal structures of solid solutions of BiMn_1−xSc_xO₃ with x=0.05, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.7 were studied with synchrotron X-ray powder diffraction. The strong Jahn-Teller distortion, observed in BiMnO₃ at 300 K and associated with orbital order, disappeared already in BiMn_0.95Sc_0.05O₃. The orbital-ordered phase did not appear in BiMn_0.95Sc_0.05O₃ down to 90 K. Almost the same octahedral distortions were observed in BiMn_1−xSc_xO₃ with 0.05?x?0.7 at room temperature and in BiMnO₃ at 550 K above the orbital ordering temperature T_OO=473 K. These results allowed us to conclude that the remaining octahedral distortions observed in BiMnO₃ above T_OO are the structural feature originated from the highly distorted monoclinic structure.     

Solid solubility and phase transitions in the system LaNb1−xTaxo4

The solid solubility between LaNbO₄ and LaTaO₄ was investigated by X-ray diffraction, and a two-phase region was observed in the composition region LaNb_1−xTa_xO₄ where 0.4?x?0.8. Single-phase LaNb_1−xTa_xO₄ (0?x?0.4) with the monoclinic Fergusonite structure at ambient temperature, was observed to transform to a tetragonal Scheelite structure by in-situ high-temperature X-ray diffraction, and the phase transition temperature was shown to increase with increasing Ta-content. This ferroelastic to paraelastic second-order phase transition was described by Landau theory using spontaneous strain as an order parameter. The thermal expansion of LaNb_1−xTa_xO₄ (0?x0.4) was shown to be significantly higher below the phase transition than above. Single-phase LaNb_1−xTa_xO₄ (0.8?x?1) with another monoclinic crystal structure at ambient temperature was shown to transform to an orthorhombic crystal structure by X-ray diffraction and differential scanning calorimetry. The phase transition temperature was observed to decrease with decreasing Ta-content. Finally, orthorhombic LaTaO₄ could also be transformed to monoclinic LaTaO₄ at ambient temperature by applying a uniaxial pressure of 150-170 MPa, reflecting the lower molar volume of monoclinic LaTaO₄.