A semi-empirical equation for oxygen nonstoichiometry of perovskite-type ceramics

Explicit equations correlating oxygen nonstoichiometry to oxygen partial pressure and temperature are important for applications of perovskite-type ceramics as membranes, adsorbents and catalysts in various chemical reaction and separation processes. A semi-empirical equation for oxygen nonstoichiometry on perovskite-type ceramics is reported in this paper. Though derived from the results of a point defect model on a perovskite-type ceramic material, La_0.1Sr_0.9Co_0.5Fe_0.5O_3−δ, this equation describes very well the experimentally measured oxygen nonstoichiometry data for two perovskite-type ceramics measured in this work and three perovskite-type ceramics reported in the literature. The major advantage of this semi-empirical equation lies in its simplicity, explicitness and accuracy. This equation is coupled with oxygen permeation equation to predict oxygen permeation current density through two perovskite-type ceramic membranes. The predicted data agree very well with the results reported in the literature using a complex defect reaction model.     

Oxygen nonstoichiometry in high-Tc superconductor HoBa2Cu3O6+x and application of coulometric tritration

Nonstoichiometry in the perovskite-type compound, HoBa₂Cu₃O_6+x, was determined as a function of oxygen partial pressure (5 × 10⁻¹ 1 × 10⁵ Pa) in the temperature range of 8631173 K by coulometric titration using a stabilized zirconia electrolyte. Electromotive force of the cell, EMF, was measured as a function of oxygen content at constant temperature, and as a function of temperature at constant oxygen content. The perovskite-type compound was found to have a tendency to decompose into Ho₂O₃, BaO, CuO and some double-oxides at low oxygen partial pressures. Defect equilibria are discussed on the basis of the dependence of nonstoichiometry on oxygen partial pressure. Variation of the relative partial molar entropy with composition is explained in terms of a well-known defect model. A new technique which was developed for measuring the electrical conductivity of a non-stoichiometric oxide, in situ, at constant oxygen content as a function of temperature in the coulometric titration cell, is presented.     

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.     

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.     

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.     

X-ray spectral and Mossbauer investigations of structure defects and the degree of inversion of manganese-zinc ferrites

X-ray and Mossbauer spectroscopy is used to investigate the effect of vacuum cooling on the valence of cations of manganese and iron, nonstoichiometry and the degree of inversion of manganese-zinc ferrites. The dependence of the valency of the cations of manganese and iron, the degree of inversion, and the degree of nonstoichiometry on the partial pressure of oxygen produced in the cooling stage is established. An interrelationship is found between the defects and the degree of inversion of manganese-zinc ferrites.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 15–18, March, 1982.     

In-situ Mössbauer spectroscopy and thermogravimetry of La0.2Sr0.8FeO3−Δ and La0.4Sr0.6FeO3−Δ

Single phase perovskite-type oxides La_0.2Sr_0.8FeO_3−Δ (LSF28) and La_0.4Sr_0.6FeO_3−Δ (LSF46) were prepared by the glycine nitrate process. The oxygen nonstoichiometry of LSF46 was studied by precision thermogravimetry at 700 and 900 °C as a function of oxygen partial pressure. Mössbauer spectra were measured at room temperature, as well as at 500 and 700 °C (LSF28) and at 700 and 900 °C (LSF46) under varying oxygen partial pressures. Good agreement is observed for the pO₂-dependent nonstoichiometry of LSF46 at 700 and 900 °C as derived from thermogravimetry and in-situ Mössbauer spectroscopy. At low pO₂, the Mössbauer isomer shifts and quadrupole splittings indicate a phase transition in LSF46 at 700 °C and in LSF28 at the two temperatures studied from a disordered perovskite phase to a brownmillerite-like structure with larger quadrupole splitting.     

Oxygen nonstoichiometry and transport properties of strontium substituted lanthanum cobaltite

Oxygen nonstoichiometry, structure and transport properties of the two compositions (La_0.6Sr_0.4)_0.99CoO_3−δ (LSC40) and La_0.85Sr_0.15CoO_3−δ (LSC15) were measured. It was found that the oxygen nonstoichiometry as a function of the temperature and oxygen partial pressure could be described using the itinerant electron model. The electrical conductivity, σ, of the materials is high (σ > 500 S cm^− 1) in the measured temperature range (650–1000 °C) and oxygen partial pressure range (0.209–10^− 4 atm). At 900 °C the electrical conductivity is 1365 and 1491 S cm^− 1 in air for LSC40 and LSC15, respectively. A linear correlation between the electrical conductivity and the oxygen vacancy concentration was found for both samples. The mobility of the electron-holes was inversely proportional with the absolute temperature indicating a metallic type conductivity for LSC40. Using electrical conductivity relaxation the chemical diffusion coefficient of oxygen was determined. It was found that accurate values of the chemical diffusion coefficient could only be obtained using a sample with a porous surface coating. The porous surface coating increased the surface exchange reaction thereby unmasking the chemical diffusion coefficient. The ionic conductivity deduced from electrical conductivity relaxation was determined to be 0.45 S cm^− 1 and 0.01 S cm^− 1 at 1000 and 650 °C, respectively. The activation energy for the ionic conductivity at a constant vacancy concentration (δ = 0.125) was found to be 0.90 eV.     

Oxygen nonstoichiometry and high temperature conductivity of the 2201 phase of the Bi---Sr---Cu---O superconducting oxide

The oxygen nonstoichiometry and high temperature conductivity of Bi_2.12Sr_1.86Cu_1.02O_y (2201 phase) were determined as a function of temperature (T) and oxygen partial pressure (P_O2). The dependences of conductivity on T and P_O2 were similar to those of oxygen content, and two subphases, and β, were found in such cases as 2212 and 2223 phases. From the result a close relationship was inferred between conductivity and oxygen content, and the mobility and carrier density were calculated. The carrier density of 2201 phase was smaller than those of the 2212 and 2223 phases.     

Oxygen nonstoichiometry and defect structure of the double perovskite GdBaCo2O6 − δ

The results of oxygen nonstoichiometry, δ, measured by means of coulometric technique as a function of oxygen partial pressure, p_O2, in temperature range 900 ≤ T °C ≤ 1050 are presented for GdBaCo₂O_6 − δ with double perovskite structure. Partial molar enthalpy and entropy of oxygen in GdBaCo₂O_6 − δ structure were calculated. Both thermodynamic properties were shown to increase dramatically in the vicinity of the oxygen nonstoichiometry value equal to 1. The p_O2 dependences of oxygen nonstoichiometry and the δ dependences of the partial molar properties were found to have inflections when the oxygen content of GdBaCo₂O_6 − δ is equal to 5.0 exactly. The modeling of the defect structure of the double perovskite GdBaCo₂O_6 − δ was carried out by considering different reference states. Only the model based on the cubic perovskite GdCoO₃ as a reference state was shown to fit the experimental data on oxygen nonstoichiometry of GdBaCo₂O_6 − δ good enough. Equilibrium constants of the appropriate defects reactions were, therefore, determined. Concentrations of all defect species defined within the framework of this model were calculated as functions of temperature and oxygen nonstoichiometry. Oxygen vacancies were shown to be formed during p_O2 diminution in gas environment in the layers of GdBaCo₂O_6 − δ crystal lattice where they are ordered until oxygen nonstoichiometry of the oxide becomes equal to unity afterwards oxygen vacancies are formed randomly in oxygen polyhedrons.     

氧分压对ZrO2薄膜激光损伤阈值的影响

 在不同的氧分压下用电子束热蒸发的方法制备了ZrO₂薄膜。分别通过X射线衍射、光学光谱、热透镜技术、抗激光辐照等测试，对所制备样品的微结构、折射率、吸收率及激光损伤阈值进行了测量。实验结果表明，薄膜中晶粒主要是四方相为主的多晶结构，并且随着氧分压的增加，结晶度、折射率以及弱吸收均逐渐降低。薄膜的激光损伤阈值开始随着氧分压增加从18.5J/cm²逐渐增加，氧分压为9×10^-3Pa时达到最大，值为26.7 J/cm²，氧分压再增加时则又降低到17.5 J/cm²。由此可见，氧分压引起的薄膜微结构变化是ZrO₂薄膜激光损伤阈值变化的主要原因。     

Influences of oxygen partial pressure on structure and related properties of ZrO2 thin films prepared by electron beam evaporation deposition

ZrO₂ thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on structure and related properties of ZrO₂ thin films were studied. Transmittance, thermal absorption, structure and residual stress of ZrO₂ thin films were measured by spectrophotometer, surface thermal lensing technique (STL), X-ray diffraction and optical interferometer, respectively. The results showed that the structure and related properties varied progressively with the increase of oxygen partial pressure. The refractive indices and the packing densities of the thin films decreased when the oxygen partial pressure increased. The tetragonal phase fraction in the thin films decreased gradually as oxygen partial pressure increased. The residual stress of film deposited at base pressure was high compressive stress, the value decreased with the increase of oxygen partial pressure, and the residual stress became tensile with the further increase of oxygen pressure, which was corresponding to the evolution of packing densities and variation of interplanar distances.     

Oxygen permeability of CaTi0.8Fe0.2O3-δ

The oxygen permeation through a dense ceramic membrane with the composition CaTi_0.8Fe_0.2O_3-δ has been measured as a function of the oxygen partial pressure gradient across the membrane at high temperatures (1000, 1050 °C). The permeation current dependence on the oxygen pressure gradient indicates that bulk diffusion controls the oxygen transport rate in the membrane under moderate oxygen pressure gradients, while the surface exchange limits the oxygen permeation at high oxygen pressure gradients. An oxygen concentration drop appears at the membrane-gas boundary.     

Defect chemistry and electrical properties of La1-xSrxCoO3-δ

This paper reports defect diagrams of Sr-doped lanthanum cobaltate, La_1−xSr_xCoO_3−δ (LSC), involving both random defect model and the cluster defect model in the temperature range between 873 K and 1173 K. The diagrams are derived in the form of defects concentrations as a function of oxygen partial pressure using the nonstoichiometry data reported in the literature. The effect of the Sr content on defect structure of LSC is discussed in terms of both defect models.     

Defect structure and oxide ion transport in Sr- and Cr-doped LaCoO3 − δ

The results of oxygen nonstoichiometry, δ, measured by means of coulometric technique as a function of oxygen partial pressure, p_o2, in temperature range 1223 ≤ T, K ≤ 1323 are presented for the perovskite-type doped with chromium solely LaCo_0.7Cr_0.3O_3 − δ and simultaneously doped both with strontium and chromium La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ cobaltites. The limit stability of the latter was found to exceed that of undoped cobaltite LaCoO_3 − δ on six orders of magnitude of p_o2 at a given temperature. The modeling of the defect structure of these perovskites was carried out and its adequate model was found. Chemical and self-diffusion coefficients of oxygen vacancies and oxygen ionic conductivity and ionic transport numbers were measured for the first time for La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ as a function of oxygen partial pressure p_o2and temperature in the ranges − 4 ≤ log(p_o2, atm) ≤ 0 and 1223 ≤ T, K ≤ 1323, respectively. The additional substitution of Sr for La in LaCo_0.7Cr_0.3O_3 − δ was shown to lead to noticeable increase of ionic conductivity and oxygen chemical diffusion coefficient at given values of oxygen partial pressure and temperature as compared to lanthanum cobaltite doped with chromium solely. Self-diffusion coefficient of oxygen vacancies and their mobility in La_0.7Sr_0.3Co_0.7Cr_0.3O_3 − δ were found to be dependent on oxygen partial pressure and nonstoichiometry unlike undoped and doped with chromium lanthanum cobaltites.     

Ionic conduction in BaxCe0.8Er0.2O3−α

Ba_xCe_0.8Er_0.2O_3−α (x=0.98–1.03) solid electrolytes were synthesized by high temperature solid-state reaction. X-ray diffraction (XRD) patterns showed that the specimens were a single perovskite-type orthorhombic phase. The conduction properties of the specimens were studied electrochemically in the temperature range of 600–1000 °C. The influence of nonstoichiometry in the specimens with x≠1 on conduction properties was investigated and compared with that in the specimen with x=1. These three specimens showed a good protonic conduction under wet hydrogen, a mixed conduction of oxide-ion and electronic hole under dry higher oxygen partial pressure, and a mixed conduction of proton, oxide-ion and electronic hole under wet higher oxygen partial pressure. Both of the protonic and oxide-ionic conductivities increased with increasing barium content in the specimens under wet hydrogen and dry air, respectively.     

Influence of Oxygen Vacancy on Transport Property in Perovskite Oxide Heterostructures

Effect of oxygen vacancy on transport property of perovskite microstructures is studied theoretically. Compared with calculated and measured I-V curves, it is revealed that electron conduction plays an important role in the oxygen nonstoichiometry perovskite heterostructures even with hole-doped or un-doped material due to the oxygen vacancies. In addition, a detailed understanding of the influence of oxygen vacancy concentration and temperature on the conduction characteristics of oxide heterojunction with both forward and reverse biases is obtained by calculation.     

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.     

氧分压对电子束蒸发SiO2薄膜机械性质和光学性质的影响

采用ZYGO MarkⅢ-GPI数字波面干涉仪、NamoScopeⅢa型原子力显微镜对不同氧分压下电子束蒸发方法制备的SiO₂薄膜中的残余应力及表面形貌进行了研究, 结果发现：随着氧分压的增大, 薄膜中的压应力值逐渐减小, 最后变为张应力状态; 同时薄膜的表面粗糙度也随着氧分压的增大而逐渐增大. 另外, 折射率对氧分压也非常敏感, 随着氧分压的增大呈现出了减小的趋势. 这些现象主要是由于氧分压的改变使得SiO₂薄膜结构发生了变化引起的.     

Study of the effect of the oxygen partial pressure on the properties of rf reactive magnetron sputtered tin-doped indium oxide films

The influence of the oxygen partial pressure on the properties of indium tin oxide films deposited by rf reactive magnetron sputtering has been studied. The oxygen partial pressure was varied from 3.2 × 10⁻⁴ to 1.0 × 10⁻³ mbar. It has been found that the 4 × 10⁻⁴ mbar of oxygen partial pressure is a critical point. When the oxygen partial pressure is lower than 4 × 10⁻⁴ mbar, the deposition rate of the films is high; the films have low transmittance and electrical resistivity; the X-ray diffraction shows that the films have a random orientation and the images of the scanning electron microscopy show that the films surface are smooth without structure. When the pressure is higher than 4 × 10⁻⁴ mbar, the deposition rate is low and does not change as the oxygen partial pressure is further increased; the transmittance and the electrical resistivity are both high; the films show the preferred orientation along the (440) direction; the films surface show a clear structure and as the pressure is increased further, the films become porous. Considering both the factor of transmittance and resistivity, the optimum oxygen partial pressure will be 3.6 × 10⁻⁴ mbar. The films prepared at this pressure have 80% transmittance and 9 × 10⁻⁴ Ω cm resistivity.