Electrical conducting properties of proton-conducting terbium-doped strontium cerate membrane

The electrical conduction behavior of SrCe_0.95Tb_0.05O_3−δ (SCTb) was investigated in different gases at high temperatures. In air, oxygen or nitrogen SCTb shows small electronic-hole conduction below 800°C and oxygen ionic conduction over 800°C with activation energy about 30 kJ/mol and 164–181 kJ/mol respectively. SCTb becomes a protonic conductor in hydrogen or methane in 500–900°C, with the proton conductivity in the range of 10⁻³–10⁻² S/cm, two to three orders of magnitude higher than electronic or oxygen ionic conductivity of SCTb in air or oxygen. The activation energy for protonic conduction in SCTb is 49 kJ/mol in methane and 54 kJ/mol in hydrogen. The electrical conductivity of SCTb in water vapor-saturated nitrogen, air or oxygen is higher than in corresponding gas without water vapor. Presence of water vapor does not affect the electrical conduction of SCTb in hydrogen or methane. Gas permeation measurements show that SCTb membrane is impermeable to hydrogen when the membrane is exposed to hydrogen or methane upstream and nitrogen or oxygen downstream. These results confirm that SCTb is a pure protonic conductor with very low electronic and oxygen ionic conductivity. SCTb will find applications as a high temperature electrolyte in fuel cells or hydrogen sensors.     

Ambipolar diffusion phenomena in BaTiO3 and SrTiO3

The electrical conductivity of resistive oxygen sensors based on semiconducting titanates (BaTiO₃, SrTiO₃) is determined by the amount and the ratio of the different concentrations of atomic defects in the sensor material. At sufficiently high temperatures the sensor exchanges oxygen with the surrounding gas atmosphere resulting in variations of the concentration of defects. The kinetics of these oxygen exchange processes are determined by the diffusion of the defects in the solid. In this paper the diffusion coefficients of the defects, which are decisive for the electrical conductivity, are determined by measurement of the conductivity during the diffusion processes. The evaluation of these results by an analytical model which considers the interaction between all simultaneously diffusing types of defects, allows a survey of the effects influencing the diffusion rate. With this knowledge, it is possible to estimate the influence of grain boundaries, acceptors, temperature and oxygen pressure on the response time of the sensor.     

Effect of uniaxial stress on ionic conductivity of 14 mol%-yttria-stabilized zirconia single crystal

In the present study, the ionic conductivity of the 14 mol%-yttria stabilized zirconia single crystal subjected to the tensile or compressive stress was examined at various temperatures. The conductivity was increased by the tensile stress and the improvement in the conductivity was higher at the lower temperature and also for the specimen with the <100> orientation. On the other hand, the conductivity was decreased by the compressive stress. The change by the compressive stress was higher at the lower temperature, but it was generally smaller than that in the tensile test. The maximum improvement achieved by applying the tensile stress was about 18% at 850 K in the present study. The present experimental results qualitatively agreed with the molecular dynamics simulations on the oxygen diffusion. The oxygen displacement in the fluorite lattice caused by the applied stress could be attributed to the change in the conductivity.     

Ionic and electronic conductivity in CaTi1−xFexO3−δ (x=0.1–0.3)

Electrical conductivity measurements on CaTi_1?xFe_xO_3?δ (x=0.1, 0.2, 0.3) were performed on polycrystalline pressed and sintered tablets using the van der Pauw four point method in controlled atmospheres. The results were interpreted to reflect n-type, ionic and p-type conductivity at different oxygen partial pressures. An increasing iron content increases the number of oxygen vacancies and increases the ionic conductivity at high temperatures, but also increases the tendency of ordering, which suppresses the ionic conductivity at more moderate temperatures. These findings are in accordance with the phase diagram of the system CaTiO₃-CaFeO_2.5 based on X-ray and Mössbauer studies.     

Ionic conductivity of ThO2- and ZrO2-based electrolytes between 300 and 2000 K

A conductivity vs temperature relationship is derived which results from simplified geometrical considerations of a polycrystalline solid electrolyte, assuming that oxygen ion diffusion only takes place through the grains or along the grain boundaries. The relationship proves to be capable of describing conductivity data of YDT, CDT, YSZ and CSZ between 300 and 2000 K. The data analysis reveals that the activation enthalpy as well as the activation entropy of grain conductivity are significantly higher in comparison with grain-boundary conductivity. It may be concluded that BAUERLE's electrical equivalent circuit which underlies the interpretation of dispersive type measurements aiming at separate determination of grain and grain-boundary conductivity ought to be revised.     

高导无氧铜的高压与高应变率本构模型研究

基于Y/G及G/B为常数的假设,构建了高导无氧铜的七种高压与高应变率本构模型.对于高导无氧铜进行了平面冲击波试验,采用纵向与横向锰铜应力计记录了试件中的纵向与横向应力,从而得到了屈服应力历史.用所构建的七种本构模型进行了数值模拟,并与高导无氧铜的平面冲击波试验结果进行比较.结果表明,平面冲击波载荷下高导无氧铜的屈服强度对于压力、密度、温度以及塑性应变的依赖性是本构描述的关键.而由Hopkinson试验取得的高导无氧铜高应变率本构模型,并不适合描述平面冲击波载荷下的本构特性. 关键词： 本构模型 高导无氧铜 平面冲击波试验 锰铜应力计     

Atomic and electronic structures of Mg-doped perfect SrTiO3 and crystals containing oxygen vacancies from first principles

The electronic properties of Mg-doped perfect SrTiO₃ and crystals containing oxygen vacancies systems are investigated by first principles calculation. Dopant formation energy results show that the Mg atoms preferentially enter the Sr site in SrTiO₃. Substitution of Ti by Mg brings some acceptor levels, which introduces the p-type conductivity of SrTiO₃. Creation of oxygen vacancies in SrTiO₃ introduces donor levels, which can contribute to the n-type conductivity. In SrTiO₃ containing oxygen vacancies system, a self-compensation effect will occur when Ti is substituted by Mg, and the system undergoes n-type to p-type transition.     

Relationship of crystal growth parameters to the stoichiometry of EuO as determined by I.R. and conductivity measurements

Single crystals of EuO have been grown from melts containing excess Eu-metal. i.r. absorption and conductivity measurements were made on these crystals and the results correlated with the crystal growth parameters. It is seen that as the concentration of europium in the initial melt is increased, the growth temperature is lowered and the crystals become richer in europium. The variations in the i.r. absorption and conductivity were studied and are shown to be strongly related to composition. According to the i.r. and conductivity behavior, the EuO crystals can be classified into five types, with compositions ranging from oxygen-rich, to stoichiometric, to europium-rich. The oxygen-rich EuO crystals are insulators and exhibit i.r. absorption which is attributed to Eu₃O₄ and to Eu³⁺. Only weak i.r. absorption is seen in the stoichiometric crystals. Those with a deficiency of oxygen show a new i.r. absorption and have either metallic conduction or show large insulator-metal transitions which are attributed to 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.     

First-principles study of the influences of oxygen defects upon the electronic properties of Nb-doped TiO_2 by GGA + U methods

The influence of oxygen defects upon the electronic properties of Nb-doped TiO2has been studied by using the general gradient approximation(GGA)+U method. Four independent models(i.e., an undoped anatase cell, an anatase cell with a Nb dopant at Ti site(NbTi), an anatase cell with a Nb-dopant and an oxygen vacancy(NbTi+VO), and an anatase cell with a Nb-dopant and an interstitial oxygen(NbTi+Oi)) were considered. The density of states, effective mass, Bader charge, charge density, and electron localization function were calculated. The results show that in the NbTi+VOcell both eg and t2glevels of Ti 3d orbits make contributions to the electronic conductivity, and the oxygen vacancies(VO) collaborate with Nb-dopants to favor the high electrical conductivity by inducing the Nb-dopants to release more excess charges. In NbTi+Oi, an unoccupied impurity level appears in the band gap, which served as an acceptor level and suppressed the electronic conductivity. The results qualitatively coincide with experimental results and possibly provide insights into the preparation of TCOs with desirable conductivity.     

Transport properties and defect analysis of La1.9Sr0.1NiO4 + δ

The oxygen flux through La_1.9Sr_0.1NiO_4 + δ has been measured as a function of oxygen activity gradient and temperature (750–1000 °C). The oxygen nonstoichiometry was determined by thermogravimetry in the temperature range of 400–1000 °C and oxygen partial pressures of 0.0002–1 atm. The total conductivity was measured over a similar range of conditions. The oxide ion partial conductivity derived from the oxygen flux data is approximately 4 orders of magnitude lower than the total, mainly p-type electronic conductivity. The defect structure was derived based on the data. Combining the oxygen flux and oxygen nonstoichiometry, the self diffusion coefficient of oxygen interstitials was evaluated.     

Relationship between the photoluminescence and conductivity of undoped ZnO thin films grown with various oxygen pressures

The pulsed laser deposition (PLD) technique is used to deposit undoped ZnO thin films on glass substrates at 150 °C with different oxygen pressures of 40, 80, 100 and 150 mTorr. X-ray diffraction (XRD) and atomic force microscopy (AFM) studies indicated that the obtained ZnO thin films were hexagonal wurtzite-type structures with strong (0 0 2) c-axis orientation. The relationship between photoluminescence and the conductivity of the ZnO thin films grown by pulsed laser deposition at various oxygen pressures was also discussed. The intensity of the deep-level-emission (DLE) and conductivity generally increased as the oxygen pressure decreased. The intensity of DLE peak was generally proportional to the conductivity. The band gap energy values, determined from transmittance spectra, were around 3.30-3.34 eV, and decreased when the oxygen pressure increased.     

Conduction in magnesium phthalocyanine thin films with aluminium electrodes

The various electrical properties and the nature of conduction mechanisms of magnesium phthalocyanine thin film devices with top and bottom aluminium electrodes have been investigated. The conduction mechanism was identified as injection limited essentially due to the electrode material. Even with the same electrode materials, the device showed asymmetric conduction behavior in the forward and reverse bias. In general the conduction was interpreted as a Schottky emission with barrier height Φ_s=1.07 eV for the forward bias and Φ_s=1.09 eV in the reverse bias. The effect of oxygen on the conductivity of the device has also been investigated. In the oxygen doped samples the conductivity is decreased which may be attributed to an interfacial layer between the electrode and the organic layer. Further in the oxygen doped sample while a Schottky emission is observed at lower voltages Poole-Frenkel conductivity was identified in the higher voltage region.     

High temperature transport processes in lithium niobate

The electrical conductivity of single crystal lithium niobate (LiNbO₃) was determined as a function of temperature for various oxygen partial pressures. The electrical conductivity is proportional to P_o2^−1/4 which can be explained by a defect equilibrium involving singly ionized oxygen vacancies and electrons.

Measurements of electrical transport numbers at 1000°K show the electrical conductivity of LiNbO₃ to be ionic at one atmosphere of oxygen and electronic at low oxygen partial pressures.

Thermoelectric measurements indicate that LiNbO₃ at low oxygen partial pressures is n-type and that the concentration of electrons at 1000°K and in an atmosphere of 50% C0/50% CO₂a is 4 × 10¹⁷cm³ with a mobility of 1.7 cm²V sec.

The diffusion of oxygen in LiNbO₃ was determined as a function of temperature at an oxygen partial pressure of 70 Torr. by measuring O¹⁸/O¹⁶ isotope exchange with the gas phase as a function of time. The diffusion data may be represented by D = 3.03 × 10⁻⁶ exp (−29.4 kcal mole⁻¹/RT)cm²sec. Consideration of the Nernst-Einstein relation for oxygen and the variation in conductivity with Li₂O activity indicate that the ionic conduction is caused by transport of lithium ions.     

Ionic and electronic conductivity in CaTi0.9fe0.1o3-δ

Abstract

The electrical conductivity of CaTi_1?x Fe _x O_3-δ (x = 0.1) was measured by an alternating current van der Pauw technique versus oxygen partial pressure (10^?30-1 atm) and temperature (450–1200°C). The results were interpreted to reflect n-type, ionic and p-type conductivity at respectively low, intermediate and high oxygen partial pressures. The apparent activation enthalpy for the ionic conductivity, interpreted to reflect the mobility of oxygen vacancies, was 0.87 eV. The enthalpy of intrinsic formation of electronic defects (apparent band gap E _g) was 3eV. The results are compared with literature data for CaTi_0.8Fe_0.2O_3-δ and with Fe-substituted SrTiO₃ and discussed in terms of iron-oxygen vacancy association and ordering.     

高氧空位浓度对金红石TiO2导电性能影响的第一性原理研究

采用基于密度泛函理论的平面波超软赝势方法研究了 纯的和不同高氧空位浓度金红石型TiO_2-x (x=0, 0.083, 0.125, 0.167, 0.25)超胞的能带结构分布、态密度分布.同时, 采用局域密度近似+U方法调准了带隙.结果表明, 高氧空位浓度越高, 金红石型TiO₂的最小带隙越变窄、电子有效质量越减小, 自由电子浓度越高, 电子迁移率越低、电导率越低.计算结果与实验结果的变化趋势相符合. 关键词： 高氧空位 2')" href="#">金红石型TiO₂ 电导率 第一性原理     

Optical properties of nonstoichiometric ZrO<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript> according to spectroellipsometry data

Amorphous nonstoichiometric ZrO_x films of different composition have been synthesized by the method of ion-beam sputtering deposition of metallic zirconium in the presence of oxygen at different partial oxygen pressures in the growth zone, and their optical properties have been studied in the spectral range of 1.12–4.96 eV. It is found that light-absorbing films with metallic conductivity are formed at the partial oxygen pressure below 1.04 × 10^–3 Pa and transparent films with dielectric conductivity are formed at the pressure above 1.50 × 10^–3 Pa. It is shown that the spectral dependences of optical constants of ZrO_x films are described well by the corresponding dispersion models: the Cauchy polynomial model for films with dielectric conductivity and the Lorentz–Drude oscillator model for films with metallic conductivity.     

Oxygen permeation studies on La0.8Sr0.2Ga0.75Mg0.15Co0.10O3±δ

Oxygen permeation measurements were carried out on La_0.8Sr_0.2Ga_0.75Mg_0.15Co_0.10O_3±δ specimens of different thickness at temperatures between 673 and 1173 K under various gradients of oxygen partial pressure. Simultaneously, the open circuit cell voltage was measured. It was shown that the investigated compositions were characterized by a high oxygen permeation rate, and, consequently, by a high electronic conductivity. The electrode polarization effect was experimentally proved, and the influence of the measurement conditions on the degree of the electrode polarization effect was studied and discussed in detail. In particular, this mentioned influence was found to be sufficiently smaller at higher oxygen partial pressures in the cathode (oxygen-rich) compartment, while the change of p_O2 on the anode (oxygen-lean) side of the permeation cell did not lead to any sufficient electrode polarization. The values of the hole conductivity calculated from the experimental results found to be at least influenced by electrode polarization were used for calculations of the hole conductivity. The comparison of these values with results obtained by other experimental techniques (by p_O2-dependence of the total conductivity measured using impedance spectroscopy and Hebb–Wagner-polarization technique) demonstrated a satisfactory agreement.     

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.     

Electronic conductivity and chemical diffusion in n-conducting barium titanate ceramics at high temperatures

The electronic conductivity as well as the chemical diffusion coefficient of barium titanate ceramics doped with Y and Mn (donor-doped and acceptor co-doped) have been determined by application of conductivity relaxation experiments. The equilibrium values of the electronic conductivity of n-conducting BaTiO₃ have been analyzed by application of a defect chemical model involving electrons and cation vacancies as the predominant defect species at oxidizing conditions (fairly high oxygen partial pressures). The relaxation curves of the electronic conductivity yield the chemical diffusion coefficient of the bulk by employing a spherical grain model where the appropriate diffusion length is the radius of grains (average grain size). The conductivity relaxation experiments have been performed as a function of temperature ranging from 1100 to 1250 °C at oxygen partial pressures between 0.01 and 1 bar. The kinetics of the oxygen exchange process can be interpreted in terms of extremely fast diffusion of oxygen via oxygen vacancies along the grain boundaries and slow diffusion of Ti (cation)-vacancies from the grain boundaries into the grains. The Ti-vacancy diffusion coefficients were extracted from the chemical diffusion coefficients as a function of temperature. Typical values for the Ti-vacancy diffusivity are around 10^− 15 cm² s^− 1 with an activation energy of 3.9 ± 0.7 eV.