Structural and electrical properties of La2−xBaxMo2O9−x/2 (x = 0-0.18)

La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) have been prepared by solid state reaction method. The lattice parameter of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) determined by XRD data refinement shows a linear dependence on the dopant Ba content x. For the specimen with a La/Ba molar ratio of 0.18-0.2, additional reflection of secondary phase exists in the XRD pattern, so the value of solubility limit for Ba in La₂Mo₂O₉ is defined in range of 0.18 < x < 0.2. As the replacement degree of La³⁺ by Ba²⁺ increases, the bulk conductivity of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) decreases initially and then increases, a minimum value at La_1.9Ba_0.1Mo₂O_8.95 exists. Hebb-Wagner studies in argon atmosphere, which use an oxide-ion blocking electrode, show that La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) are predominantly oxide-ion conducting in the temperature ranging from 773 to 1173 K. The average thermal expansion coefficient of La_1.84Ba_0.16Mo₂O_8.92 determined by high-temperature XRD was deduced as great as 17.5 × 10⁻⁶ K⁻¹ between 298 and 1173 K.     

Mixed cation effect in xR2O-(40 − x)Na2O-50B2O3-10Bi2O3 (R = Li, K) glasses

Mass density, glass transition temperature and ionic conductivity are measured in xLi₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ and xK₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ glass systems with 0 ≤ x ≤ 40 mol%. The strength of the mixed alkali effect in T_g, dc electrical conductivity and activation energy has been determined in each glass system. The magnitudes of the mixed alkali effect in T_g for the mixed Li/Na glass system are much smaller than those in the mixed K/Na glasses. The impact of mixed alkali effect on dc electrical conductivity in mixed Li/Na glass system is more pronounced than in the K/Na glass system. The results are explained based on dynamic structure model.     

Oxide-ion conductivity in CuxCe1−xO2−δ (0 ≤ x ≤ 0.10)

Up to 10 at.% of copper readily substitutes for cerium in ceria. It is found that at oxygen partial pressures between 0.21 atm and 10⁻⁵ atm, Cu_xCe_1−xO_2−δ (0 ≤ x ≤ 0.10) solid solution behave as an oxide-ion electrolyte. Interestingly, Cu_0.10Ce_0.90O_2−δ exhibits the oxide-ion conductivity of ca. 10⁻⁴ Ω⁻¹ cm⁻¹ at 600 °C at an oxygen partial pressure of 10⁻⁵ atm.     

Structural, magnetic and dielectric properties of Bi1−ySryFe(1−y)(1−x)Sc(1−y)xTiyO3 (x = 0-0.2, y = 0.1-0.3) ceramics

In this study, bulk ceramics with general formula Bi_1−ySr_yFe_{(1−y)(1−x)}Sc_(1−y)xTi_yO₃ (x = 0-0.2, y = 0.1-0.3 mol%) were prepared by traditional solid-state reaction method. As a comparison, bulk BiFeO₃ (BF) was also sintered by rapid sintering method. Their structural, magnetic, dielectric properties were investigated. X-ray diffraction analysis indicated that apart from a small amount of secondary phase detected in BF, all other samples crystallized in pure perovskite structure and maintained original R3c space group. The room temperature M-H curves were obtained. While BF had a coercive magnetic field (H_c) of 150 Oe, Bi_1−ySr_yFe_1−yTi_yO₃ solid solutions had a much larger value (for y = 0.1, 0.2, 0.3, H_c were 4537, 5230 and 3578 Oe, respectively). Sc³⁺ substitution decreased the H_c values of these solid solutions remarkably, and resulted in soft magnetic properties, as well as a decrease of the dielectric loss. At 1 MHz, the tan δ of Bi_0.7Sr_0.3Fe_0.7(1−x)Sc_0.7xTi_0.3O₃ with x = 0.05, 0.1, 0.15, 0.2 were 0.1545, 0.1078, 0.1046 and 0.1701, respectively.     

Synthesis, structural and magnetic properties of La1−xCdxFeO3 (0.0 ≤ x ≤ 0.3) orthoferrites

Nanocrystalline La_1−xCd_xFeO₃ (0.0 ≤ x ≤ 0.3) solid solutions have been synthesized by a single-step solution combustion method at a relatively low temperature of 400 °C. The combustion-synthesized solid solutions were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and magnetic measurements. The crystal structure examined by XRD indicates that the samples were single-phase, and crystallize in an orthorhombic (space group, Pbnm no. 62) structure. The parent and doped compounds showed canted antiferromagnetic behavior associated with an increase in magnetic moment with Cd doping. The changes in magnetic properties of the materials are correlated to the changes in structural features resulting from the Rietveld structural refinement of the materials.     

Structure, dielectric and ferroelectric anisotropy of Sr2−xCaxBi4Ti5O18 ceramics

Sr_2−xCa_xBi₄Ti₅O₁₈(x = 0, 0.05) powders synthesized by solid state route were uniaxially pressed and sintered at 1225 °C for 2 h. The obtained dense ceramics exhibited crystallographic anisotropy with a dominant c axis parallel to the uniaxial pressing direction which was quantified in terms of the Lotgering factor. Microstructure anisotropy of both compositions (x = 0, 0.05) consisted of plate like grains exhibiting their larger surfaces mostly perpendicular to the uniaxial pressing direction. Dielectric and ferroelectric properties of Sr_2−xCa_xBi₄Ti₅O₁₈ ceramics were measured under an electric field (E) applied parallel and perpendicularly to uniaxial pressing direction. The obtained dielectric ?_R(T) and polarization (P-E) curves depended strongly on E direction thus denoting a significant effect from microstructure and crystallographic texture. Sr_2−xCa_xBi₄Ti₅O₁₈ properties were also significantly affected by Ca content (x): Curie temperature increased from 280 °C (x = 0) to 310 °C (x = 0.05) while ?_R and remnant polarization decreased for x = 0.05. The present results are discussed within the framework of the processing and crystal structure-properties relationships of Aurivillius oxides ceramics.     

Effect of B-site doping on Sm0.5Sr0.5MxCo1−xO3−δ properties for IT-SOFC cathode material (M = Fe, Mn)

The crystal structure, thermal expansion rate, electrical conductivity and electrochemical performance of Sm_0.5Sr_0.5M_xCo_1−xO_3−δ (M = Fe, Mn) have been investigated. Two crystal structures have been observed in the specimens of Sm_0.5Sr_0.5Fe_xCo_1−xO_3−δ (SSFC) at room temperature, the perovskite structure of SSFC has an orthorhombic symmetry for 0 ≤ x ≤ 0.4 and a cubic symmetry for 0.5 ≤ x ≤ 0.9. The specimens of Sm_0.5Sr_0.5Mn_xCo_1−xO_3−δ (SSMC) crystallize in an orthorhombic structure. The adjustment of thermal expansion rate to electrolyte, which is one of the main problems of SSC, can be achieved to lower TEC values with more Fe and Mn substitution. Especially, Sm_0.5Sr_0.5Mn_0.8Co_0.2O_3−δ exhibits good thermal compatibility with La_0.8Sr_0.2Ga_0.8Mg_0.2O₃. High electrical conductivities are obtained for all the specimens and they demonstrate above 100 S/cm at 800 °C in SSFC system. The polarization resistance increases with increasing Mn content, Nevertheless, the polarization resistance of SSFC increases with increasing Fe content, but when the amount of Fe reaches to 0.4, the maximum is obtained while the resistance will decrease when the amount of Fe reaches above 0.4. Sm_0.5Sr_0.5Fe_0.8Co_0.2O_3−δ electrode exhibits high catalytic activity for oxygen reduction operating at temperature from 700 to 800 °C.     

Ba3ZnTa2−xNbxO9 and Ba3MgTa2−xNbxO9 (0≤x≤1): synthesis, structure and dielectric properties

Oxides belonging to the families Ba₃ZnTa_2−xNb_xO₉ and Ba₃MgTa_2−xNb_xO₉ were synthesized by the solid state reaction route. Sintering temperatures of 1300°C led to oxides with disordered (cubic) perovskite structure. However, on sintering at 1425°C hexagonally ordered structures were obtained for Ba₃MgTa_2−xNb_xO₉ over the entire range (0≤x≤1) of composition, while for Ba₃ZnTa_2−xNb_xO₉ the ordered structure exists in a limited range (0≤x≤0.5). The dielectric constant is close to 30 for the Ba₃ZnTa_2−xNb_xO₉ family of oxides while the Mg analogues have lower dielectric constant of ∼18 in the range 50 Hz to 500 kHz. At microwave frequencies (5-7 GHz) dielectric constant increases with increase in niobium concentration (22-26) for Ba₃ZnTa_2−xNb_xO₉; for Ba₃MgTa_2−xNb_xO₉ it varies between 12 and 14. The “Zn” compounds have much higher quality factors and lower temperature coefficient of resonant frequency compared to the “Mg” analogues.     

R3Mn1.5CuV0.5O9 (R = Y, Ho, Er, Tm, Yb and Lu) and Lu3Mn3−3xCu2xVxO9: New noncentrosymmetric oxides related to YMnO3

We report formation of new noncentrosymmetric oxides of the formula, R₃Mn_1.5CuV_0.5O₉ for R = Y, Ho, Er, Tm, Yb and Lu, possessing the hexagonal RMnO₃ (space group P6₃cm) structure. These oxides could be regarded as the x = 0.5 members of a general series R₃Mn_3−3xCu_2xV_xO₉. Investigation of the Lu-Mn-Cu-V-O system reveals the existence of isostructural solid solution series, Lu₃Mn_3−3xCu_2xV_xO₉ for 0 < x ≤ 0.75. Magnetic and dielectric properties of the oxides are consistent with a random distribution of Mn³⁺, Cu²⁺ and V⁵⁺ atoms that preserve the noncentrosymmetric RMnO₃ structure.     

Structural studies of Fe2O3-Bi2O3-CdO glass system

xFe₂O₃·(100 − x)[Bi₂O₃·CdO] system with 0 ≤ x ≤ 50 mol% was prepared and investigated by X-ray diffraction, density, FT-IR and Raman spectroscopies. The XRD patterns confirm the formation of a vitreous structure for x < 35 mol% Fe₂O₃. The evolution of density and molar volume with the addition and increasing of iron content indicates structural changes in the structure of Bi₂O₃·CdO glass matrix. The FT-IR spectrum of the glass matrix reveals a structure realized from BiO₃ pyramidal and BiO₆ octahedral units. With the addition of iron the structure proposed by the glass matrix is changing by the appearance of FeO₄ units. Also the existence of FeO₆ units cannot be excluded. The Raman spectra suggest a structure build from BiO₆ octahedral units. By Raman scattering the presence of structural units characteristic to Fe₂O₃ was not directly observed but the evolution of the spectra is dependent of the iron content.     

New substitutions and novel derivatives of the Aurivillius phases, Bi5TiNbWO15 and Bi4Ti3O12

We investigated isomorphous substitution of several metal atoms in the Aurivillius structures, Bi₅TiNbWO₁₅ and Bi₄Ti₃O₁₂, in an effort to understand structure-property correlations. Our investigations have led to the synthesis of new derivatives, Bi₄LnTiMWO₁₅ (Ln = La, Pr; M = Nb, Ta), as well as Bi₄PbNb₂WO₁₅ and Bi₃LaPbNb₂WO₁₅, that largely retain the Aurivillius (n = 1) + (n = 2) intergrowth structure of the parent oxide Bi₅TiNbWO₁₅, but characteristically tend toward a centrosymmetric/tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2Ti^IV → M^V + Fe^III in Bi₄Ti₃O₁₂, yields new Aurivillius phases, Bi₄Ti_3−2xNb_xFe_xO₁₂ (x = 0.25, 0.50) and Bi₄Ti_3−2xTa_xFe_xO₁₂ (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi₄Ti₃O₁₂. Two new members of this family, Bi₂Sr₂Nb₂RuO₁₂ and Bi₂SrNaNb₂RuO₁₂ that are analogous to Bi₂Sr₂Nb₂TiO₁₂, possessing tetragonal (I4/mmm) Aurivillius structure have also been synthesized.     

Influences of poling condition and sintering temperature on piezoelectric properties of (Na0.5Bi0.5)1 − xBaxTiO3 ceramics

The structure, ferroelectric characteristics and piezoelectric properties of (Na_0.5Bi_0.5)_1 − xBa_xTiO₃ (x = 0.04, 0.06, 0.10) ceramics prepared by conventional solid state method were investigated. The influences of poling condition and sintering temperature on the piezoelectric properties of the ceramics were examined. The piezoelectric properties of the ceramics highly depend on poling field and temperature, while no remarkable effect of poling time on the piezoelectric properties was found in the range of 5-25 min. Compared with (Na_0.5Bi_0.5)_0.96Ba_0.04TiO₃ and (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃, the piezoelectric properties of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ are more sensitive to poling temperature due to the relatively low depolarization temperature. Moderate increase of sintering temperature improved the poling process and piezoelectric properties due to the development of microstructural densification and crystal structure. With respect to sintering behavior and piezoelectric properties, a sintering temperature range of 1130-1160 °C was ascertained for (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Synthesis of non-stoichiometric Bi2O4−x by oxidative precipitation

Bi₂O_4−x, a Bi mixed-valence phase was prepared at 95 °C, by a precipitation process, in a basic medium with a highly oxidizing K₂S₂O₈/Na₂S₂O₈. This phase has a low thermal stability as it decomposes below 400 °C in a multiple step process by some O₂ losses prior to finally transforming into γ-Bi₂O₃. The as-prepared powders are 50-60 nm in size with a narrow size distribution. Optical spectra of Bi₂O_4−x exhibit a broad absorption band with a band gap of ∼1.4 eV as compared to 2.61 eV for Bi₂O₃. The composition of this non-stoichiometric phase, which crystallizes in cubic fluorite related structure with a cell parameter of 5.538(3) Å, is Bi₂O_{3.65 ± 0.10}.     

Crystal structure and electrical properties of new tungsten bronzes: BxWO3 (0.01 ≤ x ≤ 0.08)

Boron tungsten bronzes B_xWO₃ (0.01 ≤ x ≤ 0.08) were synthesized by hybrid microwave method from mixtures of WO₃ and amorphous boron powder. With the increase of boron content, the crystal structure of B_xWO₃ transforms from orthorhombic (x = 0.01) to tetragonal α (x = 0.048) and then to tetragonal β (0.07 ≤ x ≤ 0.08). The average size of crystallites is in the range of 1-10 μm. All samples show semiconducting behaviour in their temperature dependence of resistivity. The conduction behaviour above 80 K for samples with x = 0.01 and 0.08 can be explained using the variable-range hopping and thermally activated mechanism, respectively. Comparative experiments showed that boron bronze phases cannot be obtained by the microwave heating of pure WO₃ powder or a mixture of B₂O₃ and WO₃ under the same conditions.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Structural, magnetic, and electronic characterization of double perovskites BixLa2−xMnMO6 (M = Ni, Co; x = 0.25, 0.50)

A newly substituted series of perovskites, Bi_xLa_2−xMnMO₆ with M = Ni, Co and x = 0.25, 0.50, were synthesized using a citrate sol-gel technique. The crystal structure, established from neutron diffraction, is a distorted double perovskite with partial transition metal B-site ordering. These perovskites crystallize in the centrosymmetric space group, P2₁/n, with structures that are similar to the x = 0 end members. All samples are prone to non-stoichiometry involving substitution of Mn onto the Ni/Co sites, in addition to varying degrees of antisite disorder. The neutron powder diffraction and magnetization measurements reveal ferromagnetism in all samples with ordering temperatures between 220 K and 280 K. The M = Co samples have lower Curie temperatures, but higher coercivities. There is a clear link between the degree of transition metal site disorder and the saturation magnetization values. Electrical measurements demonstrate the presence of mixed ionic and electronic conductivity.     

Low loss Sr1−xCaxLa4Ti5O17 microwave dielectric ceramics

Microwave dielectric ceramics in the Sr_1−xCa_xLa₄Ti₅O₁₇ (0 ≤ x ≤ 1) composition series were prepared through a solid state mixed oxide route. All the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1450-1580 °C. Theoretical density and molar volume decreased due to the substitution of Ca²⁺ for Sr²⁺ which was associated with a decrease in the dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) but an increase in quality factor, Qf_o. Optimum properties were achieved for Sr_0.4Ca_0.6La₄Ti₅O₁₇ which exhibited, ?_r ∼ 53.7, Qf_o ∼ 11,532 GHz and τ_f ∼ −1.4 ppm/°C.     

Decomposition of (Ti2xFe1−xSb1−x)O4 solid solutions below 1673 K

The pseudo-binary TiO₂-FeSbO₄ system was investigated by means of thermogravimetric analysis below 1673 K in O₂. Rutile-type solid solutions were synthesised at 1373 K in O₂ by means of a solid state reaction between the two pure end members TiO₂ (rutile) and FeSbO₄ mixed in stoichiometric amounts. Thermal stability of the (Ti_2xFe_1−xSb_1−x)O₄ solid solution increases with rutile content; equimolar (Ti_1.00Fe_0.50Sb_0.50)O₄ solid solutions decompose at about 1673 K forming a TiO₂-enriched solid solution and FeSbO₄, that subsequently decomposes into Fe₂O₃ (hematite) and a volatile Sb oxide, probably Sb₄O₆. For compositions characterised by higher Ti content the decomposition temperature is higher than 1673 K.     

Synthesis, structure and magnetic properties of Sr2Fe1−xGaxMoO6 (0 ≤ x ≤ 0.6) double perovskites

Polycrystalline Sr₂Fe_1−xGa_xMoO₆ (0 ≤ x ≤ 0.6) materials have been synthesized by solid state reaction method and studied by neutron powder diffraction (NPD) and magnetization measurements. Rietveld analysis of the temperature dependent NPD data shows that the compounds crystallize in the tetragonal symmetry in the space group I4/m. The anti-site (AS) defects concentration increases with Ga doping, giving rise to highly B-site disordered materials. Ga doping at the Fe-site decreases the cell volume. The evolution of bond lengths and the cation oxidation states was determined from the Rietveld refinement data. The saturation magnetization and Curie temperature decreased with the increasing Ga content in the samples. Low temperature neutron diffraction data analysis and magnetization measurements confirm the magnetic interaction as ferrimagnetic in the sample.