Oxygen permeability, thermal expansion and mixed conductivity of GdxCe0.8−xPr0.2O2−δ, x=0, 0.15, 0.2

The non-linear thermal expansion behaviour observed in Ce_1−yPr_yO_2−δ materials can be substantially controlled by Gd substitution. Coulometric titration shows that the charge compensation mechanism changes with increasing x, in the system Gd_xCe_0.8−xPr_0.2O_2−δ. For x=0.15, charge compensation is by vacancy formation and destabilises the presence of Pr⁴⁺. At x=0.2, further Gd substitution is charge compensated by additionally raising the oxidation state of Pr rather than solely the creation of further oxygen ion vacancies. Oxygen concentration cell e.m.f. measurements in an oxygen/air potential gradient show that increasing Gd content decreases ionic and electronic conductivities. Ion transference numbers measured under these conditions show a positive temperature dependence, with typical values t_o=0.90,0.98 and 0.80 for x=0,0.15 and 0.2, respectively, at 950 °C. These observations are discussed in terms of defect association. Oxygen permeation fluxes are limited by both bulk ambipolar conductivity and surface exchange. However, the composition dependent trends in permeability are shown to be dominated by ambipolar conductivities, and limited by the level of electronic conductivity. At the highest temperatures, oxygen permeability of composition x=0.2 approaches that of composition x=0, Ce_0.8Pr_0.2O_2−δ, with specific oxygen permeability values approximately 2×10⁻⁹ mol s⁻¹ cm⁻¹ at 950 °C, but offering much better thermal expansion properties.     

Synthesis and electrical conductivity of perovskite-type PrCo1−xMgxO3

Oxides in the system PrCo_1−xMg_xO₃ (x=0.0, 0.05, 0.10, 0.15, 0.20, 0.25) were synthesized by citrate technique and characterized by powder X-ray diffraction and scanning electron microscope. All compounds have a cubic perovskite structure (space group ). The maximum ratio of doped Mg in the system PrCo_1−xMg_xO₃ is x=0.2. Further doping leads to the segregation of Pr₆O₁₁ in PrCo_1−xMg_xO₃. The substitution of Mg for Co improves the performance of PrCoO₃ as compared to the electrical conductivity measured by a four-probe electrical conductivity analyzer in the temperature range from 298 to 1073 K. The substitution of Mg for Co on the B site may be compensated by the formations of Co⁴⁺ and oxygen vacancies. The electrical conductivity of PrCo_1−xMg_xO₃ oxides increases with increasing x in the range of 0.0-0.2. The increase in conductivity becomes considerable at the temperatures ?673 K especially for x?0.1; it reaches a maximum at x=0.2 and 1073 K. From x>0.2 the conductivity of PrCo_1−xMg_xO₃ starts getting lower. This is probably a result of the segregation of Pr₆O₁₁ in PrCo_1−xMg_xO₃ , which blocks oxygen transport, and association of oxygen vacancies. A change in activation energy for all PrCo_1−xMg_xO₃ compounds (x=0-0.25) was observed, with a higher activation energy above 573 K and a lower activation energy below 573 K. The reasons for such a change are probably due to the change of dominant charge carriers from Co⁴⁺ to Vö in PrCo_1−xMg_xO₃ oxides and a phase transition mainly starting at 573 K.     

Structure and phase composition of nanocrystalline Ce1−xLuxO2−y

The microstructure and phase stability of nanocrystalline mixed oxide Lu_xCe_1−xO_2−y (x=0-1) are described. Nano-sized (3-4 nm) oxide particles were prepared by the reverse microemulsion method. Morphological and structural changes upon heat treatment in an oxidizing atmosphere were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman and Yb³⁺ emission spectroscopy, the latter ion being present as an impurity in the Lu₂O₃ starting material. Up to 950 °C, the samples were single phase, with structure changing smoothly with Lu content from fluorite type (F) to bixbyite type (C). For the samples heated at 1100 °C phase separation into coexisting F- and C-type structures was observed for 0.35<x<0.7. It was also found that addition of Lu strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C.     

Probing the local structure of crystalline ZITO: In2−2xSnxZnxO3 (x≤0.4)

The local structure of In₂O₃ cosubstituted with Zn and Sn (In_2−2xSn_xZn_xO₃, x≤0.4 or ZITO) was determined by extended X-ray absorption fine structure (EXAFS) for x=0.1, 0.2, 0.3 and 0.4. The host bixbyite In₂O₃ structure is maintained up to the enhanced substitution limit (x=0.4). The EXAFS spectra are consistent with random substitution of In by the smaller Zn and Sn cations, a result that is consistent with the “good-to-excellent” conductivities reported for ZITO.     

Crystal structure and electrical conductivity of lanthanum-calcium chromites-titanates La1−xCaxCr1−yTiyO3−δ (x=0-1, y=0-1)

Five series of perovskite-type compounds in the system La_1−xCa_xCr_1−yTi_yO₃ with the nominal compositions y=0, x=0-0.5; y=0.2, x=0.2-0.8; y=0.5, x=0.5-1.0; y=0.8, x=0.6-1.0 and y=1, x=0.8-1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)?1, the phase diagram of the CaTiO₃-LaCr^IIIO₃-CaCr^IVO₃ quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCr^IVO₃-CaTiO₃-LaCr^IIIO₃. The solid solution La_{(1−x′−y)}Ca_(x′+y)Cr^IV_x′Cr^III_{(1−x′−y)}Ti_yO₃ exists by up to 0.6-0.7 mol fractions of CaCr^IVO₃ (x^′<0.6-0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La_0.1Ca_0.9TiO₃, La_0.2Ca_0.8TiO₃, La_0.4Ca_0.6Cr_0.2Ti_0.8O₃ and La_0.3Ca_0.7Cr_0.2Ti_0.8O₃ in the system La_1−xCa_xCr_1−yTi_yO₃ were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO₂=6×10⁻¹⁶-0.21×10⁵ Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10⁻¹⁵-0.21×10⁵ Pa, the compounds with x>y (acceptor doped) are p-type semiconductors and those with x<y (donor doped) and x=y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite structures: [Cr³⁺]/[Cr⁴⁺] and [Ti⁴⁺]/[Ti³⁺]. The maximum electrical conductivity at 900 °C and pO₂=10⁻¹⁵ Pa was found for the composition La_0.1Ca_0.9TiO₃ (near 50 S/cm) and in air at 900 °C for La_0.5Ca_0.5CrO₃ (close to 100 S/cm).     

p-Type electron transport in La1−xSrxFeO3−δ at high temperatures

Electrical conductivity, thermopower and oxygen content were measured for La_1−xSr_xFeO_3−δ (x=0.2, 0.5, 0.9) within the oxygen partial pressure range 10⁻⁴-0.5 atm and at temperatures 750-950 °C. The dominating charge carriers under these experimental conditions are electron holes. The results of oxygen nonstoichiometry measurements are used to estimate the concentration of holes and to analyze data on conductivity and thermopower. The changes in thermopower are described by the model assuming that the number of sites accessible for migration of holes is independent on oxygen content. The mobility of electron holes is calculated, and it is found to be virtually independent on temperature in the compositions with x<0.5 while compositions with x>0.5 exhibit thermally activated mobility and mobility values about 0.1 cm² V⁻¹ s⁻¹ or smaller. It is suggested that the main contribution to the composition dependent variations in electron hole mobility are associated with Coulomb interactions at small x's, whereas at high degrees of doping the mobility of holes is most strongly affected by the increasing amount of oxygen vacancies.     

Synthesis and characterization of Ti1−2xNbxNixO2−x/2 solid solutions

Doped-rutile has been traditionally used in ceramic pigments for its intense optical properties. In this paper, we compare the classical ceramic synthesis of Ti_1−2xNb_xNi_xO_2−x/2 system with the sol-gel methodology, which allows a reduction of the anatase-rutile transformation temperature. The composition was optimised in order to obtain a unique rutile phase with the minimum amount of pollutant Ni(II) and enhanced chromatic coordinates. Incorporation of the doping ions in the rutile structure was corroborated by XRD and Rietveld refinements. The species responsible for the colour mechanism were studied by different techniques. UV-VIS spectroscopy showed the characteristic features of Ni²⁺ ions, whose existence was corroborated by EPR and magnetic measurements. From these results, (Ni,Nb)doped-TiO₂ powder samples can be now shaped as thin films, monoliths, etc. by using sol-gel methodology without modifying their properties. This study introduces new possibilities of coloured TiO₂-based solid solutions in new combined advanced applications (colouring agent and photocatalyst, etc.).     

Doping studies of the magnetic cobaltocuprate CoSr2Y2−xCexCu2O9±δ

A structural, magnetic and electronic study of the cobaltocuprate CoSr₂Y_2−xCe_xCu₂O_9±δ (x=0.5-0.8) has been performed. All materials crystallise in the orthorhombic Cmcm symmetry space group in which chains of corner linked CoO₄ tetrahedra run parallel to the 1 1 0 direction. An antiferromagnetic transition is observed for x=0.5-0.8; T_M increases with x. A change in the dimensionality of the magnetic order occurs at x=0.8 as the interchain distance increases to a critical value. There is charge transfer between the cuprate planes and cobaltate layer as Ce doping increases, so that Co³⁺ is partially oxidised to Co⁴⁺ with a concomitant reduction in the valence of Cu. Superconductivity is not observed in any of the samples and a crossover from Mott to Efros and Shklovskii variable range hopping behaviour is evidenced as x increases from 0.5 to 0.8.     

Structural characterisation of the perovskite series Sr0.9−xCaxCe0.1MnO3: Influence of the Jahn-Teller effect

Fifteen perovskite-type compounds Sr_0.9−xCa_xCe_0.1MnO₃, x=0-0.9 in steps as fine as 0.05, have been synthesised by solid state methods, and the room temperature structures characterised using X-ray synchrotron powder diffraction. At low Ca contents (x?0.45) the structures are tetragonal in space group I4/mcm and at high Ca contents (x?0.55) the compounds are orthorhombic in space group Pbnm. At room temperature these two phases co-exist in the compound with x=0.5. XANES measurements show the Ce to be present as Ce⁴⁺ in all the oxides. High temperature structures are reported for selected members.     

Study on the solid solution of YMn1−xFexO3: Structural, magnetic and dielectric properties

The solid solution of YMn_1−xFe_xO₃ (x=0.0, 0.1, 0.2, 0.3, 0.5, 1.0) was synthesized from the citrate precursor route. The hexagonal crystal structure related to YMnO₃ was stable for x?0.3. Rietveld refinement was carried out on the composition for x=0.3 and was refined to a major hexagonal phase (∼97%) with 3% of orthorhombic Y(Fe/Mn)O₃ phase. The a-axis lattice constant increases and the c-axis lattice constant decreases with x for x?0.2. The increase in the c-axis lattice constant at x=0.3 could be due to the doping of significant amount of d⁵ ion (high spin Fe³⁺ ion) in a trigonal bipyramidal crystal field. The detailed structural, magnetic and dielectric properties are discussed.     

Structural and physical properties evolution in the 6H BaRu1−xMnxO3 synthesized under high pressure

The 6H BaRu_1−xMn_xO₃ with the hexagonal BaTiO₃ structure was synthesized using high-pressure sintering method. It is found that the lattice parameter deviates from Vegard's law at x=0.3 for the solid solutions due to the charge transfer effects at B-site. The substitution of Mn for Ru cations gives rise to the short-range magnetic ordering, due to the disordered arrangement of Ru and Mn cations. The compounds are weak ferromagnetic in the x range 0.05-0.40, with the maximal Curie temperature T_c 175.2 K at x=0.10. They are of spin-glass-like magnetism at lower temperature at x?0.1. With Mn doping, the 6H BaRuO₃ transforms to a semiconductor from the primal metal at x=0.30. The resistance as a function of temperature below about 70 K follows the two-dimensional variable-range hopping conduction mechanism in BaRu_0.50Mn_0.50O₃.     

Structural investigation of KxBa1−xGa2−xGe2+xO8 solid solutions using the X-ray Rietveld method

The K_xBa_1−xGa_2−xGe_2+xO₈ (x=0.6−1.0) solid solutions undergo a structural phase transition that has a significant effect on their sintering behavior and their microwave dielectric properties. The crystal structures of both phases within the solid-solution region were determined by the Rietveld method using powder X-ray diffraction data. We found that the low-temperature-stable phase is isostructural with the pseudo-orthorhombic KGaGe₃O₈ (space group P2₁/a), while the high-temperature-stable phase has a typical monoclinic feldspar structure (space group C2/m). Due to the topological differences between the two structures, the T-O bonds within the tetrahedra must be partially recombined to make a new framework, which causes an endothermic effect during the P2₁/a to C2/m phase transition. The correlation between the crystal structures, the microwave dielectric properties and the phase-transition behaviors were discussed in terms of the crystallographic features, the lattice parameters, and the strain-induced anisotropic peak-broadening.     

Mn environment in layered Li[Mg0.5−xNixMn0.5]O2 oxides monitored by EPR spectroscopy

X-band and high-frequency EPR spectroscopy were used for studying the manganese environment in layered Li[Mg_xNi_0.5−xMn_0.5]O₂, 0?x?0.5. Both layered LiMg_0.5Mn_0.5O₂ and monoclinic Li[Li_1/3Mn_2/3]O₂ oxides (containing Mn⁴⁺ ions only) were used as EPR standards. The EPR study was extended to the Ni-substituted analogues, where both Ni²⁺ and Mn⁴⁺ are paramagnetic. For LiMg_0.5−xNi_xMn_0.5O₂ and Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂, an EPR response from Mn⁴⁺ ions only was detected, while the Ni²⁺ ions remained EPR silent in the frequency range of 9.23-285 GHz. For the diamagnetically diluted oxides, LiMg_0.25Ni_0.25Mn_0.5O₂ and Li[Li_0.10Ni_0.35Mn_0.55]O₂, two types of Mn⁴⁺ ions located in a mixed (Mn-Ni-Li)-environment and in a Ni-Mn environment, respectively, were registered by high-field experiments. In the X-band, comparative analysis of the EPR line width of Mn⁴⁺ ions permits to extract the composition of the first coordination sphere of Mn in layered LiMg_0.5−xNi_xMn_0.5O₂ (0?x?0.5) and Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂ (x>0.2). It was shown that a fraction of Mn⁴⁺ are in an environment resembling the ordered “α,β”-type arrangement in Li_1−δ1Ni_δ1[Li_{(1−2x)/3+δ1}Ni_2x/3−δ1)_α(Mn_(2−x)/3Ni_x/3)_β]O₂ (where and δ₁=0.06 were calculated), while the rest of Mn⁴⁺ are in the Ni,Mn-environment corresponding to the Li_1−δ2Ni_δ2[Ni_1−yMn_y]O₂ () composition with a statistical Ni,Mn distribution. For Li[Li_(1−2x)/3Ni_xMn_(2−x)/3]O₂ with x?0.2, IR spectroscopy indicated that the ordered α,β-type arrangement is retained upon Ni introduction into monoclinic Li[Li_1/3Mn_2/3]O₂.     

Structural and conductivity studies of Y10−xLaxW2O21

The aim of this work was to determine structural parameters of the Y_10−xLa_xW₂O₂₁ (x=0-10) solid solution series and investigate their electric properties. Crystallographic data shows a gradual increase in symmetry with increasing La content, as the structure evolves from orthorhombic, Y₁₀W₂O₂₁, towards the pseudo-cubic structure of Y₅La₅W₂O₂₁. The solubility limit of La₂O₃ was found to be 50% (x=5). Above this level two phases were observed, La₆W₂O₁₅ and (La,Y)_10+xW_2−xO_21−δ. The conductivity of Y rich samples was very low, with σ of the order 2×10⁻⁵-5×10⁻⁵ S cm⁻¹ at 1000 °C, whilst ionic conductivity was observed for most La rich doped samples. The highest conductivity was observed for La₁₀W₂O₂₁ and its doped analogues, at 1×10⁻³-5×10⁻³ S cm⁻¹ at 1000 °C. Unit cell parameters were determined as a function of temperature from 0 to 1000°C, and thermal expansion of these materials was determined from temperature studies carried out at the Australian Synchrotron facility in Melbourne, Victoria, Australia.     

Oxygen-ion and electron conductivity in Sr2(Fe1−xGax)2O5

High-temperature electrical conductivity measurements, structural data from powder X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy were combined to study the interrelationship of oxygen ion transport and p- and n-type transport in Sr₂(Fe_1−xGa_x)₂O₅, where x=0, 0.1 and 0.2. Although gallium substitution generally decreases the total ion-electron transport, the transition of the orthorhombic brownmillerite structure to a cubic phase on heating results in the recurrence of the conductivity to the same high level as in the parent ferrite (x=0). The changes of the partial contributions to the total conductivity as a function of x are shown to reflect a complicated interplay of the disordering processes that develop in the oxygen sublattice on heating in response to replacement of iron with gallium.     

Electron doping effect on structural and magnetic phase transitions in Sr2−xNdxFeMoO6 double perovskites

Polycrystalline Sr_2−xNd_xFeMoO₆ (x=0.0, 0.1, 0.2, 0.4) materials have been synthesized by a citrate co-precipitation method and studied by neutron powder diffraction (NPD) and magnetization measurements. Rietveld analysis of the temperature-dependent NPD data shows that the compounds (x=0.0, 0.1, 0.2) crystallize in the tetragonal symmetry in the range 10-400 K and converts to cubic symmetry above 450 K. The unit cell volume increases with increasing Nd³⁺ concentration, which is an electronic effect in order to change the valence state of the B-site cations. Antisite defects at the Fe-Mo sublattice increases with the Nd³⁺ doping. The Curie temperature was increased from 430 K for x=0 to 443 K for x=0.4. The magnetic moment of the Fe-site decreases while the Mo-site moment increases with electron doping. The antiferromagnetic arrangement causes the system to show a net ferrimagnetic moment.     

Chemical shifts of atomic core levels and structure of K1−xTi1−xSbxOPO4, x=0-0.23, solid solutions

Antimony-doped K_1−xTi_1−xSb_xOPO₄, x=0.23, crystals have been prepared by spontaneous nucleation from the flux in the quaternary system K₂O-TiO₂-P₂O₅-Sb₂O₅. Crystal structure observation with TEM method reveals the presence of superstructure ordering. Core level electronic parameters have been studied by X-ray photoelectron spectroscopy. Strong effect of Sb doping has been detected for inner shells of Ti⁴⁺ ions. Prominent decreasing of the binding energy difference Δ(O 1s-Ti 2p_3/2) correlates with the shortening of mean oxide bond length L(Ti−O) at x=0.23 that suggests increased ionicity of Ti−O bonds in K_1−xTi_1−xSb_xOPO₄ solid solutions.     

Zr1−xLnxW2O8−x/2 (Ln=Eu, Er, Yb): Solid solutions of negative thermal expansion-synthesis, characterization and limited solid solubility

Zr_1−xLn_xW₂O_8−x/2 solid solutions (Ln=Eu, Er, Yb) of different substitution fractions x have been synthesized. Their X-ray diffraction (XRD) patterns have been indexed and lattice parameters calculated based on the α-ZrW₂O₈ structure. The coefficients of thermal expansion (CTEs) of these solid solutions were estimated to be −10.3×10⁻⁶ K⁻¹ in temperature range of 30-100 °C. The solubility of lanthanide ions in these solid solutions decreases linearly with the increase in the radius of substituted lanthanide ions. Based on the concentration dependence of phase transition temperatures, a novel method for determination of solubility of the lanthanide ions in Zr_1−xLn_xW₂O_8−x/2 solid solutions has been developed. This method seems to be more sensitive as compared with that based on XRD technique.     

Visible light-sensitive yellow TiO2−xNx and Fe-N co-doped Ti1−yFeyO2−xNx anatase photocatalysts

Nitrogen substituted yellow colored anatase TiO_2−xN_x and Fe-N co-doped Ti_1−yFe_yO_2−xN_x have been easily synthesized by novel hydrazine method. White anatase TiO_2−δ and N/Fe-N-doped samples are semiconducting and the presence of ESR signals at g ∼1.994-2.0025 supports the oxygen vacancy and g∼4.3 indicates Fe³⁺ in the lattice. TiO_2−xN_x has higher conductivity than TiO_2−x and Fe/Fe-N-doped anatase and the UV absorption edge of white TiO_2−x extends in the visible region in N, Fe and Fe-N co-doped TiO₂, which show, respectively, two band gaps at ∼3.25/2.63, ∼3.31/2.44 and 2.8/2.44 eV. An activation energy of ∼1.8 eV is observed in Arrhenius log resistivity vs. 1/T plots for all samples. All TiO₂ and Fe-doped TiO₂ show low 2-propanol photodegradation activity but have significant NO photodestruction capability, both in UV and visible regions, while standard Degussa P-25 is incapable in destroying NO in the visible region The mid-gap levels that these N and Fe-N-doped TiO₂ consist may cause this discrepancy in their photocatalytic activities.     

Structure and conductivity of strontium-doped cerium orthovanadates Ce1−xSrxVO4 (0≤x≤0.175)

A-site substituted cerium orthovanadates, Ce_1−xSr_xVO₄, were synthesised by solid-state reactions. It was found that the solid solution limit in Ce_1−xSr_xVO₄ is at x=0.175. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I4₁/amd (1 4 1) with a=7.3670 (3) and c=6.4894 (1) Å for Ce_0.825Sr_0.175VO₄. The UV-vis absorption spectra indicated that the compounds have band gaps at room temperature in the range 4.5-4.6 eV. Conductivity measurements were performed for the first time up to the strontium solid solution limit in air and in dry 5% H₂/Ar with conductivity values at 600 °C ranging from 0.3 to 30 mS cm⁻¹ in air to 30-45 mS cm⁻¹ in reduced atmosphere. Sample Ce_0.825Sr_0.175VO₄ is redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.