Transient creep of YBa2Cu3O7−x superconductor

Rapid changes of oxygen partial pressure (P_O2) between 10³ and 2.1×10⁴ Pa have been carried out during steady-state plastic deformation of polycrystalline YBa₂Cu₃O_7−x (YBCO) at temperatures between 825 and 900°C. Transient creep was observed after such P_O2 changes. The analysis of these creep transients allowed the determination of the chemical diffusion coefficient for reequilibration, which is identical to that found from thermogravimetry and electrical conductivity experiments for oxygen vacancies.     

Mixed conductivity in SrCe0.95Yb0.05O3 protonic conductors

The results of electrical conductivity measurements on SrCe_0.95Yb_0.05O₃ under controlled oxygen partial pressure and temperature are presented. A defect model consistent with experimental results is proposed which provides for P_O2^−1/4 dependent n-type, P_o2-independent oxygen ion and P_O2^+1/4 dependent p-type conductivity components. The band gap, reduction, oxidation and ion-migration energies are determined from an analysis of the data in terms of the proposed defect model. These results suggest that some earlier data interpreted in terms of protonic conduction may require re-evaluation.     

Determination of different oxygen transport mechanisms and measurement of the oxygen ion conductivity of Y1Ba2Cu3O7−x

By undertaking AC electrochemical impedance experiments on yttria stabilised zirconia electrolytes with polished Y₁Ba₂Cu₃O_7−x electrodes, the activation energy for oxygen ion transport within the bulk of Y₁Ba₂Cu₃O_7−x, in air, over the temperature range 823 K–1043 K, was determined to be 1.50 ± 0.05 eV. At 1000 K the oxygen ionic conductivity was calculated to be around one order of magnitude lower than that in yttria stabilised zirconia. Typical calculated values were σ=5×10⁻⁵ (ω cm)⁻¹ and 6×10⁻³ (ω cm)⁻¹ at the respective temperatures 823 K and 1043 K. By employing a similar cell but with Y₁Ba₂Cu₃O_7−x paste electrodes, oxygen transfer between the Y₁Ba₂Cu₃O_7−x and the electrolyte was found to occur via a surface diffusional processes. Over the temperature range 873 K–1098 K, in air, the activation energy for in-diffusion at the surface was found to be 1.4±0.1 eV and that for out-diffusion at the surface to be 1.76±0.05 eV.     

Chemical diffusivity of BaTiO3−δ: I. Experimental determination

The chemical diffusivity of ‘undoped' polycrystalline BaTiO_3−δ was determined via a conductivity relaxation technique, at elevated temperatures (800≤T/°C≤1100) as a function of the ambient oxygen partial pressure in the range of 10⁻¹⁶≤P_O2/atm≤1 including an n- to p-type transition regime. Mathematical formulation was developed to convert conductivity relaxation to the corresponding nonstoichiometry (δ) relaxation in the transition regime. It has been found that the chemical diffusivity appears to exhibit a maximum at the n-to-p transition point where the electronic minimum conductivity falls, and that surface reaction becomes more rate-determining than diffusion as the transition point is approached from both n-type and p-type branches. Experimental details are given and the results are exhaustively compared with those reported up to date on the ‘undoped' BaTiO₃.     

Electrons and holes in undoped Nd2CuO4

Nd₂CuO_4±δ is the non-superconducting prototype of the Re_2−xM_xCuO₄t−y family (Re=Pr, Nd, Sm and M=Ceor Th) of n-type oxide superconductors. Four-probe DC conductivity, EMF in P(O₂) gradient, and thermopower measurements have been used to characterise its electric transport and defect structure between 300 and 900°C and between 5×10⁻⁴ and 1 atm oxygen partial pressure.

The results show that Nd₂CuO_4±δ can be oxygen under-stoichiometric (with n-type conductivity), near-stoichiometric, and over-stoichiometric (with p-type conductivity) in different T, P(O₂) ranges.     

Origin of cathodic degradation and new phase formation at the La0.9Sr0.1MnO3/YSZ interface

New phase formation at the La_0.9Sr_0.1MnO₃/YSZ interface and its effects on the cathodic performances were studied at 900 °C in air. The resistance caused by the interfacial product layer kept increasing with time to reach up to 40% of the total resistance after 500 h. The interfacial product was identified as La₂Zr₂O₇ by XRD measurement. The electrical conductivity of La₂Zr₂O₇ (2.4 × 10⁻⁵ S cm⁻¹ at 1000 °C), measured by AC impedance and current interruption methods, was 4 to 7 orders of magnitude smaller than those of La_0.9Sr_0.1MnO₃ electrode or YSZ electrolyte. Either the electronic conductivity or the electrochemical O₂ reduction activity of La₂Zr₂O₇ was negligible. Combining these results, a conclusion was made that the cathodic degradation comes mainly from the growth of interfacial product layer and its contribution to the cell resistance increment is ohmic in nature.     

RF-sputtered CrB2 diffusion barrier for Ni/Au Ohmic contacts on p-CuCrO2

Ohmic contacts to p-type CuCrO₂ using Ni/Au/CrB₂/Ti/Au contact metallurgy are reported. The samples were annealed in the 200–700 °C range for 60 s in flowing oxygen ambient. A minimum specific contact resistance of 2 × 10⁻⁵ Ω cm² was obtained after annealing at 400 °C. Further increase in the annealing temperature (>400 °C) resulted in the degradation of contact resistance. Auger Electron Spectroscopy (AES) depth profiling showed that out-diffusion of Ti to the surface of the contact stacks was evident by 400 °C, followed by Cr at higher temperature. The CrB₂ diffusion barrier decreases the specific contact resistance by almost two orders of magnitude relative to Ni/Au alone.     

Ionic and electronic conductivity in lead–zirconate–titanate (PZT)

Accurate impedance measurements on differently sized samples of lead–zirconate–titanate (PbZr_0.53Ti_0.47O₃, PZT) have been analyzed with a CNLS procedure, resulting in the separation of the ionic and electronic conductivities over a temperature range from 150 to 630 °C. At 603 °C the electronic conductivity shows approximately a (P_O2)^1/4 dependence, while the ionic conductivity remains constant. Below the Curie transition temperature the oxygen non-stoichiometry becomes frozen-in and the conductivities are strongly dependent on the sample history with respect to temperature sequence and ambient P_O2. A tentative interpretation assumes defect association, i.e. formation of neutral [V_Pb–V_O^··]^× complexes, and electron-hole transfer between lead sites and lead vacancies to control the oxygen ion conductivity in the tetragonal phase.

Annealing PZT-based devices at about 600 °C under low oxygen pressure (1 Pa oxygen) effectively decreases the low temperature electronic conductivity by a factor of 100 and the ionic conductivity by a factor of 10–15 with respect to normal air processing.     

Oxygen nonstoichiometry and electrical conductivity of the solid solutions La2−xSrxNiOy (0≤x≤0.5)

Oxygen nonstoichiometry and electrical resistance of a series La_2−xSr_xNiO_y solid solutions, where x=0.0, 0.2 and 0.5 in argon flows at oxygen partial pressures 1.5, 10.2, 49.2, 100 and 286 Pa within the temperature range of 20–1050°C were studied. Nickelate oxygen desorption/sorption spectra when heating–cooling at constant rate demonstrated strong dependence of cation composition of the samples. Unlike La_1.5Sr_0.5NiO_y compounds those of La₂NiO_y and La_1.8Sr_0.2NiO_y have weakly bonded oxygen, capable to exchange reversibly with the gas phase at the temperatures higher than 250°C. The equilibrium values of oxygen nonstoichiometry and specific resistance for the these nickelates were determined at 300–1050°C and p_O2=1.5–286 Pa as a functions of temperature versus oxygen partial pressure. All nickelate studied appear to be p-type conductors with metal electric conductivity at equilibrium states.     

Ionic conductivity of crystalline and glassy Mg4.5Na7(P2O7)4

In our work single crystals of Mg_4.5Na₇(P₂O₇)₄ were prepared, pulverized, pressed into pellets and sintered in order to measure the electrical conductivity of polycrystalline specimens. The conductivity was also measured on glassy specimens obtained by the melting of previously prepared crystals. The electrical conductivities at 25°C with values of the order of 10⁻¹⁶ Ω⁻¹ cm⁻¹ for polycrystalline samples and a value of the order of 10⁻¹⁴ Ω⁻¹ cm⁻¹ for glass, show that the glassy phase of Mg_4.5Na₇(P₂ because of its greater molar volume and loosely packed structure, is a better matrix for ionic motion.     

Reaction kinetics of the Pt, O2(g)|c-ZrO2 system: precursor-mediated adsorption

A micro kinetic model of the Pt, O₂(g)|c-zirconia electrode/electrolyte system was developed in state space form (model M3). The oxygen adsorption/desorption process was modeled as a precursor-mediated surface reaction. The surface diffusion of atomic oxygen and the electrochemical reduction of atomic oxygen near the three-phase boundary (tpb) were considered. It was shown that the simulated charge-transfer behavior of M3 is significantly different from models with ordinary Langmuir kinetics (model M2). The electrochemical rate constant was estimated from selected experimental data as k₁₀=(6.05±0.25)·10⁶ m³/(mol·s). From experimental results it was concluded that only one adsorbed oxygen species is relevant for the dynamic behavior. In porous Pt electrodes binary gas phase diffusion of oxygen in O₂/N₂ gas mixtures becomes relevant at oxygen partial pressures below 10⁻³ atm. The general procedure for state and parameter estimation can be well adopted for the investigation of further reaction mechanisms.     

Densification and conductivity enhancement of Na4Zr2Si3O12-based solid electrolytes using TiO2 as a sintering aid

Densification of Na₄Zr₂Si₃O₁₂ (NZS) solid electrolytes was performed by dispersing TiO₂ (0.8–5.9 wt. %, corresponding to 5–30 mol %) in NZS powders prior to sintering at 1200°C. Increases in pellet density, from ca. 65 to 94% of the theoretical (X-ray density) value, and in electrical conductivity from 10⁻⁷ to 10⁻⁶ S/cm at 50°C were observed for small additions of TiO₂, which acts as a sintering aid. AC impedance spectroscopy reveals that the enhancement is not a bulk effect but instead is associated with a reduction in inter-granular constriction resistances within porous NZS ceramics. The presence of adsorbed water species in NZS powders prepared via a sol-gel route is found to have a dramatic effect on the conductivity enhancement.     

Sr-doped LaInO3 and its possible application in a single layer SOFC

The effects of dopants on the electrical conductivity of the perovskite-type oxide LaInO₃ have been investigated. Replacement of La by Sr is the most effective way to enhance the conductivity of LaInO₃, whereas Ca substitution for In is rather difficult due to the large difference in the ion radii. The optimum composition is La_0.9Sr_0.1InO_3−δ whose maximum conductivity is 7.6×10⁻³ S cm⁻¹ at 900°C. The electrical conductivity of La_0.9Sr_0.1InO_3−δ has been measured over a wide range of oxygen partial pressure from pO₂=1 to 10⁻²⁵ atm. P-type and n-type behavior at high and low oxygen partial pressure have been observed, respectively, while at intermediate oxygen partial pressures, the electrical conductivity changes only slightly with the oxygen partial pressure. The concept of a single layer solid oxide fuel cell based on a La_0.9Sr_0.1InO_3−δ ceramic pellet has been tested. A maximum power density of 3 mW cm⁻² at 800°C was achieved when dilute H₂ and air were used as fuel and oxidizing agent, respectively.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

Conductivity anisotropy in directionally solidified CaZrO3---CaSZ and MgO-MgSZ eutectics

The results of the impedance spectroscopy measurements on eutectic samples based on zirconium oxide are presented here. Samples of CaZrO₃---ZrO₂(cubic) and MgO---ZrO₂(cubic) have been grown by a directional solidification procedure such that the different phases appear nearly oriented along the growth direction (lamellae in the system of CaZrO₃-ZrO₂(cubic) and fibers of MgO in a ZrO₂ matrix in the other system). The DC electrical conductivity has been measured by impedance spectroscopy along and across the growth axis. For CaZrO₃---ZrO₂ the coductivity is clearly anisotropic. The following values for σT have been obtained: the conductivity at 600 °C equals 2.0 × 10⁻⁶ Ω⁻¹ cm⁻¹ perpendicular to the fiber axis and 1.4 × 10⁻⁵ Ω⁻¹ cm⁻¹ parallel to it and with an activation energy of 1.3 eV for σT. For MgO---ZrO₂(cubic) the isotropic value of the conductivity at 600 °C is 10⁻⁴ Ω⁻¹ cm⁻¹ with activation energy for σT of 1.5 eV. The anisotropic conductivity in the CaZrO₃---ZrO₂ (cubic) system has been explained by a model of an ordered stacking of oxygen conducting (cubic ZrO₂) and non-conducting (CaZrO₃ or MgO) phases.     

Effects of substitution of Ti for Fe in BiFeO3 films prepared by sol–gel process

Ti substituted BiFe_1−xTi_xO_3+δ films have been prepared on indium–tin oxide (ITO)/glass substrates by the sol–gel process. The films with x=0.00–0.20 were prepared at an annealing temperature of 600 °C. X-ray diffraction patterns indicate that all films adopt R3m structure and the films with x=0 and 0.10 show pure perovskite phase. Cross-section scanning shows the thickness of the films is about 300 nm. Through 0.05 Ti substitution, the 2P_r increases to 8.30 μC/cm² from 2.12 μC/cm² of the un-substituted BiFeO₃ film and show enhanced ferroelectricity at room temperature. The 2P_r values are 2.63 and 0.44 μC/cm² for the films with x=0.01 and 0.2, respectively. Moreover, the films with x=0.05 and 0.10 show enhanced dielectric property since the permittivity increases near 150 at the same measuring frequency. Through the substitution of Ti, the leakage conduction is reduced for the films with x=0.05–0.20.     

Impedance studies on polyacrylonitrile–CuX2–DMSO (X=Cl, Br, CF3SO3) solid polymer electrolyte

A series of polyacrylonitrile–dimethylsulfoxide–CuX₂ (X=CF₃SO₃⁻, Cl⁻, Br⁻), films (foils) were prepared by means of the solution cast technique. The thickness of the foils was between 0.04 and 0.09 cm and they contained 70–80 wt.% of the solvent. Conductivities of the solid electrolytes were obtained from impedance measurements. The conductivity increases with the increase of the salt content up to 8 wt.%; at higher concentrations (>8 wt.%) the conductivity is more or less stable, and reaches, in the case of Cu(CF₃SO₃)₂ and CuCl₂, the level of ca. 10⁻³ Ω⁻¹ cm⁻¹ at room temperature. The foils based on the CuBr₂ show even higher conductivity, close to 10⁻² Ω⁻¹ cm⁻¹ at room temperature, a value comparable to that characteristic for liquid solutions. The temperature variation of the conductivity for all the systems studied is of the Arrhenius type. The activation energy, determined from linear plots lnσ=f(T⁻¹), is of the order ca. 14 kJ mol⁻¹ for the PAN/CuBr₂/DMSO and of ca. 21 kJ mol⁻¹ for the PAN/CuCl₂/DMSO and the PAN/Cu(CF₃SO₃)₂/DMSO systems.     

High TcYBa2Cu3O7−δ superconducting transition-edge microbolometers

High T_c superconducting thin film YBa₂Cu₃O_7−δ (YBCO) bolometers have been fabricated on various substrates such as MgO, LaAlO₃, YSZ and Si using laser ablation technique. Performance of these IR bolometers operating with a Joule-Thomson refrigerator has been investigated. Measurements of the responsivity and low frequency noise near T_c in the current biased YBCO bolometers show that reliable devices can be fabricated. Measured noise equivalent power (NEP), for YBCO/YSZ bolometer, reaches 6 × 10⁻¹⁰W/Hz^1/2 at 165 Hz and has a responsivity of 60 V/W with a blackbody source. This performance is comparable to that of the optimized pyroelectric detectors. The characteristics of YBCO films deposited on Si substrates reveal that superconducting thin film multi-elements or focal plane array with silicon integrated readout circuit are feasible. Such bolometers exhibit NEP of 7 × 10⁻⁹W/Hz^1/2, and significant improvement appears possible. Electrical measurements show no noticeable film degradation after the bolometer is exposed to atmosphere for three months.     

Polyacrylonitrile–sulfolane–CuX2 (X=Cl, Br, CF3SO3) solid polymer electrolyte

A series of polyacrylonitrile–sulfolane–CuX₂ (PAN–TMS–CuX₂, where X=Cl, Br, CF₃SO₃) polymer electrolytes, of thickness between 0.03 and 0.07 cm, were prepared by means of the solution cast technique. The solvent content was as high as 60–70 wt.%. Conductivities of the foils obtained from impedance measurements were of the order of 10⁻³ Ω⁻¹ cm⁻¹. Temperature variation of the conductivity for all the systems studied was of the Arrhenius type. Exchange current density at the Cuelectrolyte interface, determined from the Tafel plot, was of the order of milliampere (mA). Cyclic voltammetry showed the irreversible character of the copper plating–stripping process.     

Electrical properties of ZrO2-In2O3-Y2O3 and its application to a membrane for gas separation

Electrical properties of In₂O₃-doped yttria-stabilized zirconia (In-YSZ) were investigated. The solubility limit of In₂O₃ in YSZ (10 mol% Y₂O₃) is 17.5 mol%. The total conductivity depended on the concentration of In₂O₃. The activation energy of In-YSZ was higher than that of YSZ. From the oxygen partial pressure (P_o2) dependence of the total conductivity of In-YSZ, the electronic conductivity increased with increasing In₂O₃ concentration at low oxygen partial pressures and at high temperature. From the results, we discussed the applicability of In-YSZ to a membrane for hydrogen production from direct water splitting at high temperature.