Structural stability and conductivity of cubic (WO3)x - (Dy2O3)y-(Bi2O3)1−x−y

Isovalent rare earth oxide cubic stabilized bismuth oxides undergo an order-disorder transition of the oxygen sublattice ∼600 °C. Annealing below this temperature leads to a decay in conductivity due to ordering. We recently discovered a high conductivity Bi₂O₃ electrolyte doped with both Dy₂O₃ and WO₃ (DyWSB). The dopants were selected based on their polarizability and its effect on both structural stability and conductivity. Electrical conductivity results of the stabilized bismuth oxide system as function of temperature and time are presented. By manipulating the composition ratio of the dopants, the structural stability was enhanced resulting in a more stable conductivity.     

Direct current bias studies on (Bi2O3)0.8(Er2O3)0.2 electrolyte and Ag–(Bi2O3)0.8(Er2O3)0.2 cermet electrode

20 mol% erbia stabilized bismuth oxide (ESB) in the cubic fluorite structure is one of the highest oxygen ion conductors known. On annealing at temperatures below the transition temperature (∼600 °C), a fast continuous decay in oxygen ion conductivity occurs which has been attributed to the occupational and positional ordering on the oxygen ion sublattice. The reverse transition is characterized by the enthalpy required to disorder the ordered lattice. This study looked into the effect of direct current bias on the ordering kinetics of ESB solid electrolytes using symmetrical cells consisting of Ag–ESB cermet electrodes. Electrochemical impedance spectroscopy studies showed that on isothermal annealing at 500 °C, the current bias does not have a significant effect on the conductivity decay, though the differential scanning calorimetry (DSC) studies showed that under bias the endotherm related with the reverse transition appeared at shorter annealing time periods. Ag–ESB electrodes showed good performance, though were unstable at 625 °C under higher bias currents due to the Ag electromigration along with the oxygen flux.     

Study of phase transition of TiO<Subscript>2</Subscript>–CaO system

Electrical conductivity of TiO₂ doped with CaO has been measured at different temperatures for various molar ratios. The conductivity after initially remaining constant till about 140 °C increases with temperature due to the migration of vacancies created by doping. After attaining a maximum value at 240 °C, conductivity decreases due to the collapse of fluorite framework. A second rise in conductivity at high temperature beyond 400 °C indicates the phase transition of TiO₂, from anatase to rutile, which is confirmed by the differential scanning calorimetry results. X-ray powder diffraction, impedance measurements, and Fourier transform infrared spectral studies were also carried out for confirming the doping effect and phase transitions in TiO₂. Doping of TiO₂ with CaO shifts the transition to lower temperatures.     

Manifestation of a Photorefractive Effect in the Raman Scattering Spectra of Lithium Niobate Crystals of Variable Composition

Using the Raman scattering spectra, we investigated the ordering of the structural units in the cation sublattice and the photorefractive properties of lithium niobate single crystals of variable composition, i.e., nominally pure ones with different Li/Nb ratios and those doped with the nonphotorefractive cations Mg²⁺, Gd³⁺, and Y³⁺. It is shown that at low concentrations of Mg²⁺, Gd³⁺, and Y³⁺ the magnitude of the photorefractive effect is substantially determined by the ordering of the structural units of the cation sublattice. It has been found for the first time that the intensity of the line corresponding to the bridge valence vibrations of oxygen atoms in the octahedrons of NbO₆ is sensitive to the dipole ordering of the cation sublattice of the crystal. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 611–614, September–October, 2005.     

Effect of ionic polarizability on oxygen diffusion in δ-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> from atomistic simulation

The effect of polarizability of cation dopants on oxygen diffusion in δ-Bi₂O₃ is determined using molecular-dynamics simulation in which the polarizability of the ions is treated within the shell model. It is found that the magnitude of the oxygen polarizability has no affect on diffusion. However, the high cation polarizability, associated with the lone pair of electrons in Bi, is found to be the key to achieving sustained oxygen diffusion. Consistent with earlier experimental results, the oxygen diffusion path is found to be between oxygen equilibrium sites, which are displaced from the 8c oxygen sites of the fluorite lattice.     

Neutron diffraction study of the oxide conducting δ1-phase of (Bi2O3)1−x(Y2O3)x (x=0.25)

The atomic parameters of the average cell of δ¹-Bi(Y)O_1.5 were determined by powder neutron diffraction. The evidence indicates that the disorder in the structure has many features in common with the structure of the oxygen deficient zirconia. Most oxygens (78%) are in sites displaced 0.335 Å along 〈100〉 directions from the normal fluorite positions, while a smaller proportion (22%) are displaced 0.80 Å along 〈111〉 directions and no oxygen remains in normal positions. In addition to the anion displacements a smaller displacement (0.25 Å) along the 〈111〉 direction was found for the cations. Comparison with the structure of β-Bi₂O₃ suggests that the displacements may be precursors to a δ→β phase transition.     

Observation of cation reordering during the olivine-spinel transition in fayalite by in situ synchrotron X-ray diffraction at high pressure and temperature

The olivine-spinel phase transition in fayalite at high pressure and temperature has been studied using time-resolved x-ray diffraction. Structure refinements show a delay of cation reordering relative to anions during the phase transformation and an increase in the cell volume while the cations reorder into their sites. A significant stress drop in the sample is observed. This experiment, for the first time, quantitatively demonstrates a pseudomartensitic transformation: a diffusionless anion sublattice transition coupled with short-range diffusional cation reordering.     

Structural study and electrical properties of Zr-doped Nd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> pyrochlore compounds

Nd₂Sn₂O₇ pyrochlores with the substitution of Zr⁴⁺ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen positional parametersx = 0.331 and 0.375, while Rietveld refinements were employed for neutron diffraction data. The neutron diffraction study revealed that there are only two anion sites with 48f and 8b positions. This indicates that the 8a site, i.e. O(3) sublattice, is completely vacant and the structure is a perfect cubic pyrochlore with space group Fd3m (O _h ⁷ ). From the conductivity measurements, it is observed that the electronic conductivity dominates from room temperature up to about 525 K and forT > 525 K, the oxygen ion conduction dominates the charge transport in these compositions. Complex impedance spectroscopy indicates the existence of grain and grain boundary as two separate elements.     

Oxide ion transport in highly defective cubic stabilized zirconias

Ac impedance spectroscopy and neutron powder diffraction have been used to study the high temperature behaviour of defective fluorite solid electrolytes. In yttria-stabilised zirconia with an yttrium content of 15 mol% YO_1.5 there is a marked change in conductivity behaviour at around 650 °C, with a decrease in activation energy of 0.15 eV. Structural studies confirm that this is due to a change in the bulk of the sample with the disappearance of diffuse scattering peaks and marked changes in the behaviour of the isotropic temperature factors at the same temperature. These results indicate that the change in activation energy of yttria-stabilised zirconia at 650 °C is due to an order-disorder transition involving local defect clusters. In studies of zirconia co-doped with yttrium and niobium, activation energy for conduction is found to rapidly increase with the concentration of the trivalent yttrium Saturation doping is reached at about 20–30 % of yttrium and activation energy only increases slightly with doping. Introduction of pentavalent niobium at this level of doping serves to decrease activation energy, although it also decreases conductivity slightly. The low and high temperature activation energies converge as the saturation regime is approached. These observations seem to suggest that ordering of defect clusters into microdomains increases activation energy for ionic motion. At low defect concentrations and high temperatures, this local ordering breaks down and the activation energy for conduction decreases. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Two-mode nature of the Raman spectrum of lithium niobate crystals

The ordering of the host and impurity cations in nominally pure (with different values of Li/Nbratio) and doped lithium niobate crystals is studied using Raman spectroscopy. It is shown that depending on the composition-controlled ordering of structural units of the cationic sublattice the crystal may exhibit, in the region of bridge stretching vibrations of the oxygen ions, either single-mode or two-mode behavior. The nominally pure lithium niobate crystals show, within the homogeneity region, single-mode behavior, while the crystals doped with divalent or trivalent cations show single-mode behavior at low concentrations of the dopant and two-mode behavior at higher concentrations.     

Oxygen thermodynamics and ion conductivity in the solid solution La1−xSrxCoO3−δ at large strontium content

The equilibrium oxygen content was measured in the model system and important oxygen permeable material La_1−xSr_xCoO_3−δ, where x=0.6, in the temperature range 650–900 °C and oxygen partial pressure range between 10⁻⁵ and 1 atm. The data were utilized to obtain changes in the partial entropy and enthalpy of oxygen in the solid as a function of the oxygen content. It is shown that the initially cubic perovskite undergoes to a phase transition to a tetragonal structure at δ >0.3. The oxygen permeation of L_0.4Sr_0.6CoO_3−δ at 700–900 °C is found to be controlled by bulk solid state processes. The activation energy equals about 0.8 eV at high oxygen pressure and small oxygen nonstoichiometry. Increasing oxygen deficiency results in a rapid increase in the activation energy. In combination with thermodynamic data, these changes can be explained as resulting from the intrinsic spatial inhomogeneouty in oxygen vacancy distribution which varies both with temperature and oxygen nonstoichiometry. It is shown that, when the oxygen deficiency increases at constant temperature, the oxygen vacancies form locally ordered microdomains (clusters), which eventually results in a transition of the cubic perovskite structure to the tetragonal structure. The oxygen ion conductivity depends strongly on the development of the ordering. Paper presented at the 6th Euroconference on Solid state Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Nanocomposites comprised of doped cerium dioxide and lanthanum manganite for syngas production

Nanocomposites comprised of fluorite-like (Gd- or Pr-doped ceria) and perovskite-like (LaMnO_3+δ) phases were prepared using a polymerized precursor (Pechini) route. Genesis of the structure of composites with annealing temperature has been studied by X-ray diffraction, Transmission Electron Microscopy and EXAFS. Up to 1300 °C, particle sizes of both fluorite and perovskite phases remain in the nano-range. Interaction between components is reflected in the increase of doped ceria lattice parameter and disordering of Mn coordination sphere. Despite this interaction, nanocomposites possess a high conductivity along with a high lattice oxygen mobility and reactivity. The addition of CoO improves sintering of nanocomposites.     

Kinetic demixing in yttria-doped zirconia part II - theoretical analysis

This paper presents a formal analysis of the transport processes in yttria-doped zirconia under a temperature gradient. Due to the simultaneous diffusion and drift of the species when the material is exposed to a thermodynamical potential gradient, a kinetic demixing process appears on the cationic sublattice if the diffusion coefficients of the cations are different. Experimental results obtained with yttria-doped zirconia are discussed on the basis of this analysis. They confirm that kinetic demixing processes during cooling must be taken into account in the interpretation of the grain boundary conductivity of doped zirconia. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

A study of iso- and alio-valent cation doped Ag2SO4 solid electrolyte

2 SO₄. The solid solubility limits up to x≤3 mole% for monovalent, x≤5.27 mole% for divalent and x≤3.63 mole% for trivalent cation doped Ag₂SO₄ are set with XRD, SEM, IR and DSC techniques. A predominant dependence of conductivity on the ionic size of iso- and alio-valent cations is observed. In particular, the conductivity enhances in both α and β phases, despite having a lower ionic-size dopant cation (relative to that of Ag⁺) in the transition element cation doped Ag₂SO₄. Ca²⁺, Ba²⁺, Y³⁺ and Dy³⁺ doped samples show depature from the regular behaviour in the β-phase. The conductivity behaviour is discussed considering ionic size, valence and electronic structure of the guest cations. Received: 3 February 1997/Accepted: 27 May 1997     

Oxygen ion conductivity in doped Gd2Ti2O7 with the pyrochlore structure

Materials with the A₂B₂O₇ pyrochlore structure have interesting ionic transport properties because of their crystallographic structure, which can be described as a stable array of corner-shared BO₆ octahedra that is penetrated by a 3-dimensional tunnel configuration that is partly filled by the A₂O sublattice. The pyrochlore stochiometry means that there are built-in intrinsic oxide ion vacancies in the crystal structure in comparison to the related fluorite type structure. These are in the A₂O sublattice, so that the tunnels are only 75% occupied. The presence of these tunnels leads to the possibility of significant changes in the composition, and some ionic species in this sublattice exhibit high mobility. The cubic pyrochlore Gd₂Ti₂O₇ was doped in various ways to change its ionic and electronic transport properties. The total conductivity and partial ionic and electronic contributions were investigated by ac impedance and EMF measurement techniques. The influence of either A or B site doping with aliovalent ions that occupy sites in the A₂O and B₂O₆ sublattices was investigated. The results of these experiments are presented and discussed in relation to the crystal structure and defect chemistry of this family of oxides. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Thermal stability and impedance spectroscopy studies of (Cu, Ni) substituted Bi4V2O11 ceramics

Polycrystalline samples of the oxygen ion conductor Bi₂V_0.9Cu_0.1−xNi_xO_5.35 with various contents of nickel (0 ≤ × ≤ 0.1) were investigated. The X-ray powder diffraction revealed the tetragonal structure of all compositions. DTA curves exhibit effects due to phase transition, one endothermic effect during heating and one exothermic one during cooling. The impedance of the ceramics with Pt electrodes was measured in the frequency range 10⁻¹–10⁷ Hz at constant temperatures between 350 and 920 K. The conductivity was determined by nonlinear least-squares analysis of the impedance spectra. Separation of the total resistance into grain interior and grain boundary components was feasible at temperatures below 580 K. The transition temperatures observed in DTA coincide with those observed in conductivity measurements. A phase transition, involving a reordering process of the oxygen ions is considered to be responsible for this phenomenon. The frequency dependent part of the intragrain conductivity was modeled by a constant phase admittance. The effective hopping rate was estimated by comparing the frequency dependent part and the dc limit of the intragrain conductivity. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997.     

Impedance study of BIMGVOX ceramics

The polycrystalline samples of Bi₂V_0.9Mg_0.1O_5.35 were synthesised. The conductivity of the samples with Pt electrodes was determined by non-linear least-squares analysis of the impedance spectra. The total conductivity of the samples exhibits Arrhenius-type dependence on temperature with two straight line sections. In the transition from one linear section to the other a time dependence of conductivity was observed. The conductivity decreases both on heating and cooling during several hours at constant temperature (between 665 and 680K and between 710 and 695K on heating and cooling respectively). During heating at temperatures between 685 and 790K the Arrhenius plot are not linear. It may be expected that a process of slow ordering/disordering of oxygen vacancies is responsible for this phenomenon. The values of conductivity at low temperatures were dependent upon the length of time the sample was allowed to reach equilibrium - the structure of the material seems to be frozen in a metastable state, probably β type. At high temperature region the conductivity do not depend on the thermal history of sample. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Crystal growth and dielectric, mechanical, electrical and ferroelectric characterization of n-bromo succinimide doped triglycine sulphate crystals

Single crystals of triglycine sulphate (TGS) doped with n-bromo succinimide (NBS) were grown at ambient temperature by the slow evaporation technique. An aqueous solution containing 1-20 mol% of n-bromo succinimide as dopant was used for the growth of NBSTGS crystals. The incorporation of NBS in TGS crystals has been qualitatively confirmed by FTIR spectral data. The effect of the dopant on morphology and crystal properties was investigated. The cell parameters of the doped crystal were determined by the powder X-ray diffraction technique. The dielectric constant of NBS doped TGS crystal was calculated along the ferroelectric direction over the temperature range of 30-60 °C. The dielectric constant of NBSTGS crystals decrease with the increase in NBS concentration and considerable shift in the phase transition temperature (T_C) towards the higher temperature observed. Pyroelectric studies on doped TGS were carried out to determine the pyroelectric coefficient. The emergence of internal bias field due to doping was studied by collecting P-E hysteresis data. Temperature dependence of DC conductivity of the doped crystals was studied and gradual increase in the conductivity with the increase of dopant concentration was observed. The activation energy (ΔE) calculated was found to be lower in both the ferroelectric and the paraelectric phases for doped crystals compared to that of pure TGS. The micro-hardness studies were carried out at room temperature on thin plates cut perpendicular to the b-axis. Less doped TGS crystals show higher hardness values compared to pure TGS. Piezoelectric measurements were also carried out on 010 plates of doped TGS crystals at room temperature.     

High-temperature behaviour of average structure and vibrational density of states in the ternary superionic compound AgCuSe

Results of simultaneous thermal analysis (STA), synchrotron powder diffraction (in the range 300–973 K) and inelastic neutron scattering (at 285 and 505 K) on non-superionic β- and superionic α-AgCuSe are reported. The sample is stable in argon on heating. The volume change at the superionic phase transition is about 5%. A model for the average structure of α-AgCuSe is proposed. No anomalies in the temperature dependence of the parameters of the average structure were revealed. Ionic conductivity in α-AgCuSe can originate from cation jumps in “skewed” 〈100 〉 directions between nearest-neighbour tetrahedral sites via the peripheries of the octahedral cavities. A correlation between the temperature dependence of the cation redistribution in α-AgCuSe and the temperature dependence of the ionic conductivity is supposed. Various contributions (anharmonic effects, time-average static disorder and phonon-phonon scattering) to the widths of individual phonons upon temperature increase lead to pronounced changes in the neutron-weighted densities of states of β- and α-AgCuSe and accompany the superionic phase transition as well.     

Response of La0.8Sr0.2CoO3-δ to perturbations on the CoO3 sublattice

Emission and transmission M?ssbauer studies of La_0.8Sr_0.2CoO_3-δ perovskites doped with ∼0.02 stoichiometric units of oxygen vacancy or 2.5% iron corroborate the occurrence of electronic phase separation in these systems. The effect of the small perturbation of the CoO₃ sublattice with either iron ions or oxygen vacancies on the bulk magnetization as well as on the M?ssbauer spectra is in good agreement with the double exchange based cluster model. The magnetoresistance does not show any peak near the Curie temperature, but reaches -84% in a field of 7.5 T at T = 8 K. Below T_C ≈ 180 K the M?ssbauer spectra distinctly include the contribution from paramagnetic and ferromagnetic regions, providing direct evidence for phase separation. No contribution to the spectra from Fe⁴⁺ ions can be observed, which is an unambiguous evidence that at low concentration iron (either directly doped or formed from ⁵⁷Co by nuclear decay) is accommodated in the cobaltate lattice as Fe³⁺ ion.