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     

Ion transport studies in zinc/cadmium halide doped silver phosphate glasses

A number of samples of silver phosphate glasses Ag₂O−P₂O₅−Zn/CdX₂ (X=Cl, Br or I) with 1, 5, 10 and 20 mol-% zinc or cadmium halides have been prepared. Control samples of undoped silver phosphate glasses were also prepared. These glasses were characterized by elemental analysis, X-ray diffraction, IR spectra, differential scanning calorimetry, transference number measurements and electrical conductivity studies. These glasses were found to be essentially ionic conductors. The undoped silver phosphate glass (Ag₂O−P₂O₅) has a low σ value in comparison to the doped ones. The conductivity (σ) in the doped glasses increases substantially with increasing concentration of dopant salts Zn/or CdX₂ and as the anions of the dopants are changed from Cl⁻ to I⁻. It is found that the σ values of the ZnX₂ doped glasses are slightly greater than those of the CdX₂ doped ones, and the silver phosphate glasses doped with (20 mol-%) Zn/CdI₂ yielded maximum conductivity. The results have been discussed and explained on the basis of changes in the structure of the glass matrix by the addition of dopant ions of different sizes, IR spectra and thermal studies.     

Reference electrode formation in potentiometric CO2 sensors with alkali ion conducting alumosilicate glasses as solid electrolytes

Potentiometric CO₂ gas sensors with Li conducting glasses/glass ceramics of the system Li₂O-Al₂O₃-SiO₂ (different nominal composition) as solid electrolytes have been investigated. Li₂CO₃ was used as CO₂ and O₂ sensitive auxiliary electrode. During the sensor test measurements, the CO₂ partial pressure was varied between 1×10⁻³ and 1×10⁻¹ bar at a constant O₂ partial pressure of 2.1×10⁻¹ bar whereas N₂ was used as carrier gas. Comparative measurements were accomplished with sensors comprising Na and K ion conducting glasses. A metastable reference electrode was formed at the contact zone between the Au metal electrode and the former Li glasses of definite nominal composition by crystallization processes taking place, which lead to stable, reproducible CO₂ dependent EMF signals for more than 90d. The thermodynamically expected EMF difference and the observed EMF difference agree quite well between 500 and 600 °C. At 600 °C, the drift of sensors with glasses as solid electrolytes and direct Au glass/glass ceramics contact as reference electrode amounts typically 0.32 mV/d (p(CO₂)=1×10⁻³ bar, p(O₂)=2.1×10⁻¹ bar at the measuring electrode), if a metastable multiphase equilibrium is formed. At identical partial pressures of CO₂ and O₂, the signal reproducibility of these sensors with different solid electrolyte glasses of the same nominal composition lies within 30 mV at 600 °C. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Electrical characterization of highly Titania doped YSZ

The defect fluorite region of the ternary system ZrO₂-Y₂O₃-TiO₂ encompasses compositions which offer both, good electronic and oxygen ion conductivity which enable good catalytic activity for the direct oxidation of methane in a solid oxide fuel cell (SOFC). The electrical properties of compositions Y_xTi_yZr_1−(x+y)O_2−x/2 (with x=0.15, 0.2, 0.25 and y=0.15, 0.18) were characterised in order to find the composition with highest ionic and electronic conductivity. High titanium dopant concentrations (Y) of 15 and 18 atom%, near the solubility limit of Ti⁴⁺ in the fluorite structure, have been introduced to achieve a high electronic conductivity at low oxygen partial pressure. The yttrium content x has been varied between 15 and 25 atom% to find the fluorite composition with the highest ionic conductivity for each titanium level. In the pO₂-range from 0.21 to 10⁻¹³ atm the conductivity is predominantly ionic and constant over that range. The maximum ionic conductivity is 0.01 Scm⁻¹ for the compositions, which contain 15 atom% yttrium. Substantial electronic conductivity is introduced into the system at low oxygen pressures below 10⁻¹³ atm via reduction of Ti⁴⁺ ions to Ti³⁺. The maximum electronic conductivity of 0.2 Scm⁻¹ at 930 °C has been measured for a sample with 18 atom% titanium. The slope of all log(σ) vs. log(pO₂) plots follows a pO ₂ ^−1/4 -dependence. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

The rate constants of singlet oxygen collision-induced emission at 634 and 703 nm wavelengths

Absolute spectral luminosity from an O₂–O₂(a)-H₂O gas flow formed by a chemical singlet oxygen generator was measured at 600–800 and 1230–1310 nm wavelengths. The results were used to determine the rate constants for O₂(a, 0) + O₂(a, 0) → O₂(X, 0) + O₂(X, 0) + hν (λ = 634 nm) and O₂(a, 0) + O₂(a, 0) → O₂(X, 1) + O₂(X, 0) + hν (λ = 703 nm) collision-induced emission ((6.72 ± 0.8) × 10⁻²³ and (7.17 ± 0.8) × 10⁻²³ cm³/s, respectively).     

Electrical properties of a new Ag+ ion conducting glassy system: x[0.75AgI:0.25AgCl] : (1−x)[Ag2O : P2O5]

A new fast Ag⁺ ion conducting glassy system: x[0.75AgI:0.25AgCl]: (1−x)[Ag₂O: P₂O₅], where 0.1 ≤ x ≤ 1 in molar weight fraction, has been synthesized by melt-quench technique using a high-speed twin roller-quencher. An alternate host salt: ‘quenched [0.75AgI: 0.25AgCl] mixed system/ solid solution’, has been used in place of the traditional host AgI. The compositional dependence conductivity studies on the glassy systems: x[0.75AgI:0.25AgCl]: (1−x)[Ag₂O: P₂O₅] as well as xAgI: (1−x)[Ag₂O: P₂O₅] prepared identically, indicated that the composition at x=0.75 exhibited the highest room temperature conductivity. The composition: 0.75[0.75AgI: 0.25AgCl]: 0.25[Ag₂O: P₂O₅] has been referred to as optimum conducting composition (OCC). The study also revealed that the new/ alternate host yielded better electrolyte system. The activation energy (E_a), involved in the thermally activated conductivity process has been computed from ‘log σ − 1/T’ Arrhenius plot. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Electrical transport properties of CuWO4

The temperature dependence of the electrical conductivity, thermoelectric power and dielectric constant of the antiferromagnetic CuWO₄ have been studied in the temperature range 300–1000 K. The conductivity results can be summarised by the equations σ_I=6.31 × 10⁻³ exp (−0.29 eV/kT) ohm⁻¹ cm⁻¹ in the temperature range 300–600 K and σ_II=3.16 × 10⁵ exp (−1.48 eV/kT) ohm⁻¹ cm⁻¹ between 600 K and 1000 K. The thermoelectric power can be expressed byθ=[− 1.25 (10³/T) + 3.9] mV/K. Initially dielectric constant increases slowly but for high temperatures its increase is fast.     

Determination of absorption cross sections for oxygen molecules in the Schumann-Runge band region at high temperatures

We have measured the absorption cross sections of oxygen molecules in oxygen and in an oxygen-argon mixture heated by a shock wave, in the wavelength range 190–250 nm at temperatures of 1500–7000 K, for thermal equilibrium conditions behind the shock wave front. Analysis of the absorption cross sections obtained allowed us to select a data set that adequately describes the absorption characteristics of the electronic transition X³Σ _g ⁻ → B³Σ _u ⁻ for the oxygen molecule. In order to approximate the temperature dependence of these cross sections at a temperature of 1500–4500 K, we chose the function σ(λ, T) = σ₀(λ)(1 − exp (−θ/T)) exp (− n*θ/T) where θ₀ = 1.4·10⁻¹⁷, 1.4·10⁻¹⁷, 1.2·10^{− 17}, and 1.3·10⁻¹⁷ cm², n* = 3.1, 4.1, 5.6, and 7.47 for wavelengths 190, 210, 230, and 250 nm, respectively; θ = 2240 K is the characteristic temperature of the O₂ molecules. The approximation error was 19–25% and did not exceed the experimental error. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 13–17, January–February, 2006.     

Defects and transport in SrFe1−xCoxO3−δ

The non-stoichiometry and chemical diffusion coefficient of SrFe_1−xCo_xO_3-δ have been measured by steady state and transient thermogravimetry in the temperature range 750–1200 °C at different oxygen partial pressures. At high oxygen partial pressures, the chemical diffusion coefficient was in the range 1·10⁻⁴ – 7·10⁻⁴ cm²/s. This, combined with high concentration of disordered vacancies make these materials perhaps the fastest solid oxygen ion diffusers known at high temperatures and high oxygen partial pressures. However, due to the high concentration of defects in SrFe_1−xCo_xO_3-δ the compound transforms from a cubic (disordered) perovskite to a brownmillerite type of structure under reduced oxygen partial pressures below approx. 900 °C. Due to this phase transition, the mobility of oxygen vacancies in SrFe_1−xCo_xO_3-δ decreases up to about an order of magnitude at 850 °C. We also observe an ordering effect at 1000 °C, although smaller in size, and this is suggested to be due to short range ordering of four-coordinated polyhedra of Fe. For possible use as oxygen separation membranes, phase stability against sulphur and carbon containing atmospheres is also discussed with respect to the formation of carbonates and sulphates. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Study on structural, thermal, sintering and conductivity of Cu-Co doubly substituted Bi4V2O11

Doubly substitution of vanadium by Cu and Co in the limit of 10% in Bi₄V₂O₁₁, has led to the formation of the Bi₄V_1.8Cu_0.2−xCo_xO_10.7 solid solution. X-ray diffraction shows that all the compositions present a tetragonal symmetry. The thermal analysis has revealed that the polymorph γ' phase, which is formed by a partial ordering of oxygen ions in the γ high temperature form, is stabilized at room temperature. The influence of sintering temperature on the microstructure of the samples was investigated by the scanning electron microscopy (SEM). The ceramics sintered at 820 °C for more than 3 hours present micro-craks. The evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance spectroscopy. The sample with x=0.1 presents the highest value of the conductivity ≈4.6×10⁻² S·cm⁻¹ at 600 °C.     

One-dimensional ionic conduction in solid Ag2 Tl6I10

The ionic and electronic conductivities of Ag₂Tl₆I₁₀ single crystals have been studied as a function of crystallographic orientation and temperature from 20 to 135°C. EMF as well as AC and DC techniques have been employed. The highly anisotropic material is predominantly an Ag⁺-ion conductor parallel toc-direction, with the Ag⁺ ions moving through linear channels that are not interconnected. The conductivity σ_‖c =1.6×10⁻⁷Ω⁻¹cm⁻¹ at 25°C, with an activation enthalpy for σ_‖c of 0.38 eV. The conduction perpendicular toc-direction has been found to be predominantly electronic with a value of σ_⊥c =3×10⁻⁹Ω⁻¹cm⁻¹ at 25°C and an activation enthalpy for σ_⊥c of 0.64 eV. This is the first observation of one-dimensional Ag⁺ conduction and this type of orientation-dependent change from ionic to electronic conduction. On leave from Institute of Physics, Academia Sinica, Peking, China.     

The superconducting properties of YBa2(Cu1−xMx)3O7 for M=Zn and Ni

Transverse and zero-field μSR measurements were made on YBa₂(Cu_1−xNi_x)₃O_7−y withx=0.1 and 0.2, and YBa₂(Cu_1−x Zn _x )₃O_7−y withx=0.03, 0.06, 0.1, and 0.16, wherey≈0.1. Since doping may lead to magnetic ordering this was searched for with both zero and transverse field μSR, but no evidence was found over the temperature range studied: 10–100 K. However, depolarization rates as functions of temperature were obtained, and the low temperature values of these are σ=3.2 μs⁻¹.1.6μs⁻¹, and 1 μs⁻¹ forx=0.01, and 0.2 Ni, respectively, and σ=0.8 μs⁻¹, 0.75 μs⁻¹, 0.65 μs⁻¹, and 0.4 μs⁻¹ forx=0.03, 0.06, 0.1, and 0.16 Zn, respectively. Estimates for the effect of decreasing electron concentration for Zn are made, but these alone do not account for the drop in σ. Estimates for the effect of scattering on λ and hence σ are made. The reduction in σ for Ni dopant is in surprisingly good agreement with these estimates. For Zn the order of magnitude is correct, but the relative lack of further change in σ after the effect of the first 0.03 addition seems to imply a saturation of the effect of scattering.     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Potentiometric CO2 - sensors with ion - conducting glasses as solid electrolytes

Alkali-ion conducting glasses/glass ceramics of the system Me₂O-A1₂O₃-SiO₂ (Me=Li, Na) were applied as solid electrolytes in potentiometric gas sensors to detect CO₂ in the presence of O₂ at increased temperatures. The corresponding Me-Carbonates were utilized as auxiliary electrodes. Sensors using the direct Au-glass contact as a kind of reference electrode (type I), as well as symmetrical sensors with carbonate phase at the reference and measuring electrode (type II - for comparative measurements) were manufactured. By applying Au as electrode metal, the theoretically expected EMF difference and the observed EMF difference of both sensor types agree quite well with the expected values according to the Nernst equation between 500 and 600 °C (over four orders of magnitude of CO₂ partial pressure (10⁻⁵ – 10⁻¹ bar) at constant O₂ partial pressure (2.1×10⁻¹ bar)). A long time stability of 120 days for sensors of type I with Li glasses has been observed, although evaporation of carbonate phase (Li₂CO₃) was detected under the conditions of sensor application. Sensors of type I (with Li₂CO₃) show thermodynamically unexpected cross-sensitivities to H₂O. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

High-temperature study of SrFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3−<Emphasis Type="Italic">z</Emphasis></Subscript> perovskites

The structure of high-temperature SrFe_{1 − x} Mo _x O_{3 − z} (0 ≤ x ≤ 0.5) phases was studied. Such studies are necessary to understand the mechanism of oxygen transport in membrane materials used for high-temperature oxygen separation.     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

High-temperature electrical transport in Al-doped calcium and strontium titanates

The electrical conductivity of perovskite-related oxides CaTi_1−xAl_xO_3−δ and SrTi_1−xAl_xO_3−δ (x=0−0.4) were investigated within the temperature range 900 to 1000 °C and the oxygen partial pressure range between 10⁻²⁰ and 0.21 atm using a dc four-point technique. The materials investigated show predominantly p-type electronic conductivity at high, n-type electronic conductivity at low, and ionic conductivity at intermediate oxygen partial pressures. The values of ionic conductivity in CaTi_1−xAl_xO_3−δ were found to be lower than those in CaTi_1−xFe_xO_3−δ. The effect of aluminium concentration on the high-temperature transport properties was examined. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Phase equilibria in the La-Me-Co-O (Me=Ca, Sr, Ba) systems

The phase equilibria of the La-Me-Co-O systems (Me = Ca, Sr and Ba) were studied in air at 1100 °C. Two types of solid solution of general composition La_1−xMe_xCoO_3−δ and (La_1−y Me_y)₂CoO₄ were found to exist in the systems. The limiting composition of La_1−xMe_xCoO_3−δ lies at x=0.8 for Me = Sr, Ba and between 0.3–0.5 for Me = Ca. It is shown that the rhombohedral distortion of the perovskite type La_1−xMe_xCoO_3−y decreases while x increases. La_1−xMe_xCoO_3−δ (Me = Sr, Ba) shows an ideal cubic structure at x=0.5. The stability range of (La_1−yMe_y)₂CoO₄ was found to be 0.25≤y≤0.35 for Me = Ca, 0.3≤y≤0.55 for Me = Sr and 0.3≤y≤0.375 for Me = Ba. All phases have tetragonal K₂NiF₄-type crystal structure. Based on the XRD and neutron diffraction patterns of quenched samples, the phase diagrams (Gibbs triangles) are constructed for all systems. The phase equilibrium at low oxygen pressure is shown for the example of the La-Sr-Co-O system. The decomposition mechanism of La_1−xSr_xCoO_3−δ at 1100 °C for the samples with 0.5<x<0.8 within the oxygen pressure range −0.678>log(Po₂)>−2.25 can be written as follows: La_1−x′ Sr_x′CoO_3−δ′=n La_1−x″Sr_x″CoO_3−δ″+m SrCoO_2.5+q/2 O₂ where x′>x″. The decomposition mechanism of La_1−xSr_xCoO_3−δ for the samples with x < 0.5 within the oxygen pressure range −2.25>log(Po₂)>−3.55 changes and can be written as follows: La_1−xSr_xCoO_3−δ′=r La_1−x′Sr_x′CoO_3−δ″+w (La_1−y′Sr_y′)₂CoO₄+v CoO+f/2 O₂. The results are shown in “logPo₂-composition” diagrams. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Study of high-temperature oxygen permeability in Sr1 ? xLaxCo0.8 ? yNbyFe0.2O3 ? z perovskites

The oxygen permeability of ceramic SrCo_{0.8 − y} Fe_0.2Nb _y O_{3 − z} (0 ≤ y ≤ 0.2) and La_0.3Sr_0.7Co_0.6Fe_0.2Nb_0.2O_{3 − z} disc membranes as a function of temperature and oxygen partial pressure was studied. Kinetic analysis was performed based on the experimental data on oxygen permeability as a function of oxygen partial pressure.     

Electron-stimulated desorption of negative O? ions from the oxidized O/Ru surface

This paper reports on a study of the electron-stimulated desorption of negative oxygen ions from the O/Ru surface, which represents an additional factor responsible for the destruction of the protective oxide layer of the mirrors used in ultraviolet lithography. The cross section of degradation of the O/Ru layer due to the electron-stimulated desorption of the O⁺ and O⁻ ions and the O atoms has been found to be 1.6 × 10⁻¹⁹ cm². A comparison of the dependences of the electron-stimulated desorption yield of O⁺ and O⁻ ions on the incident electron energy E with the ionization cross section of the adsorbate core level σ _O2s (E) has revealed that the ionization of the O 2s level is the main channel of the electron-stimulated desorption of O⁻ ions.