Impedance and electron diffraction studies on single crystals of BINIVOX

Single crystals of the nominal composition Bi₂V_0.9Ni_0.1O_5.35 were prepared. They were studied by TGA/DTA, impedance spectroscopy and electron diffraction. The impedance of the crystals with Pt electrodes was measured in two directions: parallel and perpendicular to the layers of the intergrowth structure in the frequency range 10⁻²−10⁷ Hz at temperatures between 300 and 940 K. Arrhenius type plots for both directions show two linear regions with different activation energies. In the low temperature region the conductivity in the direction parallel to the layers was by a factor of about 1000 larger than in the perpendicular direction. In the high temperature region the ratio of conductivities was about 100. A time dependence of the conductivity in the perpendicular direction was observed during heating and cooling in limited temperature ranges. The electron diffraction experiments gave evidence that the superlattice spots present in the diffraction patterns at low temperature, disappear reversibly at temperatures higher than 650 K. The transition temperatures observed in the DTA and in the electron diffraction experiments correspond to the temperature of changes of the activation energy. An order-disorder transition of oxygen ions is considered to be responsible for this phenomenon. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Magnetic and structural transitions in La1−x Sr x MnO3: T-x phase diagram

The electrical conductivity, magnetic susceptibility, magnetization, and submillimeter (v=5∓20 cm⁻¹) permittivity and dynamic conductivity of La_1−x Sr _x MnO₃ (0≤x≤ 0.45) single crystals are investigated. The anomalies in the temperature dependences of these quantities are identified with diverse magnetic and structural phase transformations, including antiferromagnetic and ferromagnetic ordering, structural transitions between strongly distorted (Jahn-Teller) and weakly distorted (pseudocubic) orthorhombic phases, structural transitions to a rhombohedral phase and unusual transitions to a polaron-ordering state. As a result, the complete T-x phase diagram of the system La_1−2x Sr _x MnO₃ is constructed in a wide interval of temperatures T=4.2∓1050 K and concentrations x=0−0.45. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 4, 331–336 (25 August 1998)     

Structural studies and ionic conductivity of CuCr1−xVxS2 (0 ≤ × ≤ 0.3)

CuCr_1−xV_xS₂ (0 ≤ × ≤ 0.3) is isostructural with CuCrS₂. The substitution of Cr by V results in the partial transition of Cu atoms into the disordered state and in an increasing Cu⁺ ion conductivity.     

Transmission spectra of epitaxial layers of Pb1 ? xEuxTe (0 ≤ x ≤ 0.37) solid solutions in the frequency range 7–4000 cm?1

The spectra of epitaxial Pb_{1 − x} Eu _x Te (0 ≤ x ≤ 0.37) solid solution layers grown on BaF₂ and Si substrates have been investigated over a wide frequency range 7–4000 cm⁻¹ at temperatures of 5–300 K. Apart from the phonon and impurity absorption lines, the absorption in a local mode in PbEuTe layers of substrates and buffer layers has been observed in the frequency range 110–114 cm⁻¹. As the temperature decreases from 300 to 5 K, the transverse phonon mode softens from 33.0 to 19.5 cm⁻¹.     

Anomalies of the pyroelectric and dielectric properties of ferroelectric ceramics of the PbZr1- x Ti x O3 system with 0.06 ≤ x ≤ 0.35 at the R3 c ? R 3 m phase transition

The temperature dependences of the pyroelectric and dielectric properties of ferroelectric ceramics of the PbZr_{1 − x} Ti _x O₃ binary system with x = 0.06, 0.07, 0.08, 0.1, 0.15, 0.2, 0.25, 0.3, and 0.35 have been obtained synchronously for each sample in the range of the structural phase transition between the states with the symmetry space groups R3c ↔ R3m. It is established that the temperatures of this phase transition for unpolarized and polarized samples coincide in the range 0.06 ≤ x ≤ 0.15. In this case, the x−T phase diagram, constructed on the basis of the pyroelectric and dielectric data, is in excellent agreement with the X-ray diffraction data on single crystals in this concentration range. The effect of dc electric fields from 5 × 10⁵ V m⁻¹ did not lead to any temperature shifts of the R3c ↔ R3m phase transition for the compositions with 0.06 ≤ x ≤ 0.25. Original Russian Text ? Yu.N. Zakharov, A.G. Lutokhin, N.A. Korchagina, V.G. Kuznetsov, 2008, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2008, Vol. 72, No. 4, pp. 589–591.     

Ferroelectric phase stabilization, phase transformations and?thermal properties in (1? x )PbZrO3– x Pb(Co1/3Nb2/3)O3 solid solution

The solid solution between the antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Co_1/3Nb_2/3)O₃ (PCoN) was synthesized by the columbite method. The phase structure and thermal properties of (1−x)PZ–xPCoN, where x=0.0–0.3, were investigated. With these data, the ferroelectric phase diagram between PZ and PCoN has been established. The crystal structure data obtained from XRD indicates that the solid solution PZ–PCoN, where x=0.0–0.3, successively transforms from orthorhombic to rhombohedral symmetry with an increase in PCoN concentration. The AFE→FE phase transition was found in the compositions of 0.0≤x≤0.10. The AFE→FE phase transition shift to lower temperatures with higher compositions of x. The width of the temperature range of FE phase was increased with increasing amount of PCoN. It is apparent that the replacement of the Zr⁴⁺ ion by (Co_1/3Nb_2/3)⁴⁺ ions would decrease the driving force for antiparallel shift of Pb²⁺ ions, because they interrupt the translational symmetry. This interruption caused the appearance of a rhombohedral ferroelectric phase when the amount of PCoN was more than 10 mol%.     

Nanosized ceria-based ceramics: a comparative study

Ce_(1−x)Gd/Sm _x O_2−δ (x = 0.05–0.2, GDC/SDC) nanometric powder was prepared by glycine-nitrates combustion synthesis, by strictly following uniformity in the preparation route. The thermochemical properties of the obtained precursor were studied by TGA/DTA. Crystallization of the fluorite phase occurred on heating at 800 °C or higher temperature. The grain size of calcined powder was found to be about 15 nm. Densification was studied as a function of dopant content. SDC was found more sinterable than GDC. Crystal structure and microstructure were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrical characterization was carried out using the impedance spectroscopy method in the frequency range of 50 Hz–13 MHz. The bulk conductivity of SDC is higher than GDC pellet for all concentration ranges. The results were analyzed by using the concept of change of the chemical bond ionicity due to the replacement of the host by dopant. Guest/host ionic size, valence mismatch ratio and their consequences are counted semiquantitatively into the configurational and thermal entropy.     

Lithium ion conductivity of Li5+xBaxLa3?xTa2O12 (x?=?0–2) with garnet-related structure in dependence of the barium content

The stoichiometry range and lithium ion conductivity of Li_5+x Ba _x La_3−x Ta₂O₁₂ (x = 0, 0.25, 0.50, 1.00, 1.25, 1.50, 1.75, 2.00) with garnet-like structure were studied. The powder X-ray diffraction data of Li_5+x Ba _x La_3−x Ta₂O₁₂ indicated that single phase oxides with garnet-like structure exist over the compositional range 0 ≤ x ≤ 1.25; while for x = 1.5, 1.75 and 2.00, the presence of second phase in addition to the major garnet like phase was observed. The cubic lattice parameter increases with increasing x and reaches a maximum at x = 1.25 then decreases slightly with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. The impedance plots of Li_5+x Ba _x La_3−x Ta₂O₁₂ samples obtained at 33 °C indicated a minimum grain-boundary resistance (R _gb) contribution to the total resistance (R _b + R _gb) at x = 1.0. The total (bulk + grain boundary) ionic conductivity increases with increasing lithium and barium content and reaches a maximum at x = 1.25 and then decreases with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. Scanning electron microscope investigations revealed that Li_6.25Ba_1.25La_1.75Ta₂O₁₂ is much more dense, and the grains are more regular in shape. Among the investigated compounds, Li_6.25Ba_1.25La_1.75Ta₂O₁₂ exhibits the highest total (bulk + grain boundary) and bulk ionic conductivity of 5.0 × 10⁻⁵ and 7.4 × 10⁻⁵ S/cm at 33 °C, respectively.     

Synthesis and electrical characterisation of the perovskite niobate-titanates,Sr1−x/2Ti1−xNbxO3−δ

The synthesis and electrical characterisation over a range of oxygen partial pressures (10⁻²⁰ to 1 atm) are reported for the cubic perovskite niobate-titanates Sr_1−x/2Ti_1−xNb_xO_3−δ, which are proposed as potential anode materials for solid oxide fuel cells. Single phase samples were observed for 0≤x≤0.4, and phase purity was retained on annealing at both high and low oxygen partial pressures. Good electrical conductivity was observed on reduction in low oxygen partial pressures, with a maximum for the sample with 25% Nb (x=0.25), σ=5.6 Scm⁻¹ at 930°C (P (O₂)=10⁻¹⁸ atm). For dense samples the higher the Nb content the more resistant the reduced sample was to reoxidation as the oxygen partial pressure was increased. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Thermal stability and electrical conductivity of multiferroics BiFeO<Subscript>3</Subscript>/REEs

Ceramic samples of bismuth ferrite and solid solutions of Bi_{1 − x} A _x FeO₃ type (where A = Lu, Yb, Tm, Er, Ho, Dy, Tb, Gb, Eu, Sm, Nd, Pr, La; 0.05 ≤ x ≤ 0.20; Δx = 0.05) were prepared. Spectra of the real part of electrical conductivity were studied within the range 10⁻⁴–10⁻⁶ Hz. The dependence of the samples’ thermal stability and electrical conductivity on the size of the substituting ions was established.     

Study on phase stabilization and electrical performance of BICO0.20−xNIxVOX solid electrolyte

BICO_0.20?xNI_xVOX solid electrolyte in the composition range 0 ≤ x ≤ 0.20 was synthesized by standard solid-state reactions. The influence of Ni substitution for Co on the relationship between the phase stabilization and electrical performance was investigated by means of X-ray powder diffraction (XRPD), differential thermal analysis (DTA) and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.13 whose thermal stability increases with Ni content. On the other hand, complex plane plots of impedance suggested a major contribution of polycrystalline grain interiors to the overall electrical conductivity and the fastest oxygen-vacancy diffusion in the perovskite vanadate layers at x = 0.13. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. However, a maximum ionic conductivity at lower temperatures (～2.56 × 10^?4 S cm^?1 at 300 °C) was observed for the composition with x = 0.13.     

Correlation between phase structure and electrical conduction in BISNVOX system for intermediate temperature solid oxide fuel cells (IT-SOFC)

Samples of Sn⁴⁺-substituted bismuth vanadate, formulated as Bi₄Sn _x V_{2? x} O_{11?( x /2)? δ} in the composition range 0.07 ≤ x ≤ 0.30, were prepared by standard solid-state reactions. Sample characterization and the principal phase transitions (α ? β, β ? γ and γ′ ? γ) were investigated by FT-IR spectroscopy, X-ray powder diffraction, differential thermal analysis (DTA) and AC impedance spectroscopy. For composition x = 0.07, the α ? β and β ? γ phase transitions were observed at temperatures of 451 and 536°C, respectively. DTA thermograms and Arrhenius plots of conductivities revealed the γ′ ? γ phase transition at 411 and 423°C for x = 0.20 and 0.30, respectively. AC impedance plots showed that conductivity is mainly due to the grain contribution, which is evident in the enhanced short-range diffusion of oxide ion vacancy in the grains with increasing temperature. The highest ionic conductivity (5.03 × 10^?5 S cm^?1 at 300°C) was observed for the x = 0.17 solid solution with less pronounced thermal hysteresis.     

Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.     

Synthesis and conductivities of the apatite-type systems, La9.33+xSi6−yMyO26+z (M=Co, Fe, Mn) and La8Mn2Si6O26

Apatite-type oxides of formula (La/Sr)_10−xSi₆O_26+y have been attracting significant interest recently, because of their high oxide ion conductivity. In this paper we report the synthesis and conductivities of phases based on doping La_9.33Si₆O₂₆ with Co, Fe, Mn on the Si site, according to the formula La_9.33+x/3Si_6−xM_xO₂₆ (M=Co, Fe, Mn). Substitution limits observed were x≤1.5 (Co), x≤1.25 (Fe), x≤0.5 (Mn). Higher Mn levels could be achieved by substituting onto the La site, with it being possible to prepare the phase La₈Mn₂Si₆O₂₆. The highest conductivities were observed for the Co doped samples, although investigations into the dependence of conductivity on p(O₂) (0.2–10⁻⁵ atm.) indicated that the conductivity was dominated by the electronic component in these cases. In contrast, the conductivities for the Fe and Mn doped samples were mainly ionic in the same p(O₂) range. Experiments into varying the oxygen content of these doped phases indicated that increasing the oxygen content above the nominally stoichiometric O₂₆ appears to increase the oxide ion conductivity. Preliminary studies of the reactivity of the electrolyte La_9.33Si₆O₂₆ with potential SOFC cathode materials (La_1−xSr_xMO₃; M=Co, Fe, Mn) suggests that reaction can occur at high temperatures leading to the incorporation of the transition metal into the apatite electrolyte. However, the fact that these doped phases exhibit high conductivities suggests that this may limit any problems caused by such a reaction at the electrolyte-electrode interface. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

The NASICON solid solution Li1−x La x /3Zr2(PO4)3: optimization of the sintering process and ionic conductivity measurements

The Li_1−x La _{x /3}Zr₂(PO₄)₃ NASICON-type compounds (0 ≤ x ≤ 1) have been synthesized in powder form by a sol-gel method and sintered for ionic conductivity measurements. In order to improve the compactness of the ceramic without decomposition of the compound, several sintering processes have been tested for one member of the solid solution (x = 0.6): the use of sintering aids (ZnO, B₂O₃, TiO₂ and LiNO₃), a ball-milling of the synthesized powder, a flash heating, high isostatic pressure, and spark plasma sintering. Finally, a satisfactory compactness of 85% is obtained compared to the referenced value (63%) obtained by uniaxial and isostatic pressing. The ionic conductivity study was performed by impedance spectroscopy. It shows that, despite the formation of vacancies, the substitution Li⁺→ 1/3 La³⁺ + 2/3 □ has unfortunately no influence on the conduction for 0 ≤ x ≤ 0.7 since the ionic conductivity remains identical to the LiZr₂(PO₄)₃ one. For higher x values, the ionic conductivity strongly decreases.     

Amorphous-to-crystalline transition in Ge22Se78−x Bi x system

Summary Crystallization kinetics is studied in glassy Ge₂₂Se_78−x Bi _x (0≤x≤10) using isothermal annealing at various temperatures between the glass transition and melting. D.c. conductivity is taken as a parameter to estimate the extent of crystallization (α). The activation energy of crystallization (ΔE) and the order parameter (n) are calculated by fitting the values of α in Avrami’s equations of isothermal transformation. The results indicate that ΔE is highly composition dependent and decreases as the Bi concentration increases.     

Study on electrical conductivity and phase transition in singly doped BIPBVOX (Bi2V1−xPbxO5.5−x/2) solid electrolyte

Samples of bismuth lead vanadium oxide (BIPBVOX) (Bi₂V_1–xPb_xO_5.5–x/2) singly substituted system in the composition range 0.05 ≤ x ≤ 0.20 were prepared by sol–gel synthesis route. Structural investigations were carried out by using a combination of differential thermal analysis (DTA) and powder X-ray diffraction (PXRD) technique. Energy dispersive X-ray spectroscopy analysis (EDXA) of doped samples was carried out to predict the sample purity and doping concentration. Transitions, α?β, β?γ and γ′?γ were detected by XRD, DTA and variation in the Arrhenius plots of conductivity. The ionic conductivity was measured by AC impedance spectroscopy. The solid solutions with composition x ≤ 0.07 undergo α?β phase transition, at 329 °C and β?γ phase transition at 419 °C. The highly conducting γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.17 whose thermal stability increases with Pb content. At 300 °C, the highest value of conductivity 6.234 × 10^?5 S cm^?1 was obtained for composition x = 0.15 and at 600 °C the highest value of conductivity 0.65 S cm^?1 is observed for x = 0.17. AC impedance plots reveal that the conductivity is mainly due to the grain contribution to oxide ion conductivity.     

Synthesis and electrical characterisation of different doped magnesium titanates

The synthesis and characterization are reported for the cubic spinel titanate Mg_(2−x)Ni_xTiO₄ (x≤0.25) and Mg_(2−x)Mn_xTiO₄ (x≤1). Single phase samples were observed for Mg_(2−x)Ni_xTiO₄ and with x≤0.4 for Mg_(2−x)Mn_xTiO₄. AC measurements were carried out on four different compositions (x=0.01, 0.03, 0.04 and 0.15) in the Mg_(2−x)Ni_xTiO₄ series and for Mg_1.9Mn_0.1TiO₄. For all these compounds, increasing conductivity with temperature and Arrhenius conductivity dependence are observed, the activation energy is around 0.28 eV for the Ni compounds and is 0.184 eV for Mg_1.9Mn_0.1TiO₄. The DC conductivity was recorded over a range of oxygen partial pressures (10⁻¹⁹ to 1 atm) at 930 °C. The Mg_(2−x)Ni_xTiO₄ compounds show a n-type behaviour whereas the Mg_(2−x)Mn_xTiO₄ show a p-type behaviour at high p(O₂) and n-type at low p(O₂). The stability under reduced conditions was checked and discussed for the different synthesized compounds. Paper presented at the 5th Euroconference onSolid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Morphotropic phase boundary, weak ferromagnetism, and strong piezoelectric effect in Bi1 ? xCaxFeO3 ? x/2 compounds

The crystal structure and magnetic and piezoelectric properties of the Bi_{1 − x} Ca _x FeO_{3 − x/2} system (x ≤ 0.2) are studied. The crystal-structure transformations occur in the following sequence: rhombohedral (R3c) polar phase (x ≤ 0.06) → modulated polar phase (0.07 ≤ x ≤ 0.1) → modulated antipolar phase (0.11 ≤ x ≤ 0.14). The modulated polar and antipolar phases are weakly ferromagnetic with a spontaneous magnetization of 0.25 G cm³/g (x = 0.09). In the polar weak ferromagnet with x = 0.09, a uniform piezoelec- tric response 2.5 times stronger than in the initial BiFeO₃ compound is detected by the piezoelectric force microscopy.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.