Oxygen permeation in bismuth-based materials. Part I: Sintering and oxygen permeation fluxes

Oxygen permeation measurements were performed on two layered bismuth based oxide ceramics: a rhombohedral phase belonging to the Bi₂O₃–CaO system, (Bi₂O₃)_0.73–(CaO)_0.27 (BICAO) and a BICOVOX phase. Oxygen permeability for these systems was compared to permeability of the cubic fluorite type structure with composition (Bi₂O₃)_0.75(Er₂O₃)_0.25 (BE25). Low oxygen permeability was observed for the pure ceramic. As for BE25, permeability was considerably increased if 40 vol.% of silver was added to BICAO. In contrast, permeability was not improved by addition of gold to BICOVOX. For this latter phase, the oxygen molecular exchange at the surface is clearly the limiting step in the oxygen transfer.     

New solid electrolytes based on bismuth oxide

The oxide ion conducting systems Bi₂O₃-Y₂O₃-Pr₆O₁₁ and Bi₂O₃-Y₂O₃-ZrO₂ have been prepared and studied in order to combine the advantages of stabilized Bi₂O₃ and ZrO₂ solid electrolytes. Coprecipitation of high purity oxides was used for preparation. The formation of the fluorite-type cubic structure was confirmed by X-ray powder diffraction analysis. The relative contributions of ions and electrons to the total conductivity were measured by the concentration cell method. Using Ultraviolet Photoemission Spectroscopy (UPS) we have determined the work function Φ of electrons, the position of the Fermi level in relation to the valence band edge (E_F-E_V) and the change of the ionization potential (I) as a function of temperature. For bismuth oxide-based solid electrolytes, we used an Fe/FeO mixture as reference contact to establish a defined oxygen partial pressure in the solid electrolyte sample. Oxygen isotope exchange experiments were performed in an exchange cell with a gas regulating system and mass spectrometer to determine the oxygen surface exchange rate. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Sonochemical preparation of bismuth oxide nanotiles decorated exfoliated graphite for the electrochemical detection of imipramine

This work described the sonohydrolysis of Bi(NO₃)₃ into Bi₂O₃ and simultaneous sonochemical exfoliation of graphite into graphene sheets in the alkaline environment and its electocatalytic performance towards the detection of anti-depression drug imipramine (IMPR). The ultrasound (37/80 kHz; 60 W) effectively hydrolyzed the Bi(NO₃)₃ into a single crystalline monoclinic phase of Bi₂O₃ nanotiles in the alkaline condition. And also, the sonochemical reaction condition can trigger the lamellar particles on the graphite bulk surface and allowed to exfoliated the graphite (EG) into graphene nanosheets as well. The material characterizations are done by XRD, Raman, FESEM, and HRTEM. It shows the α-Bi₂O₃ nanotiles along with EG nanosheets with high crystallinity and low defects. The (0 0 2) plane in XRD confirms the high crystalline nature of EG. The monoclinic stretching vibrations (90–600 cm⁻¹) confirms the Raman modes of Bi₂O₃. The prepared Bi₂O₃-EG composites are subjected to the electrochemical determination of IMPR which revealed appreciable analytical performances. The results showed that the Bi₂O₃-EG exhibits better results in the 3 h sonication process. Bi₂O₃-EG-3 exhibited a good linear range (0.02–82.3 µM) and an acceptable limit of detection (6 nM). And also Bi₂O₃-EG-3 exhibits the significant tolerance limit when compared to other potential interfering compounds.     

Electrical properties of triple-doped bismuth oxide electrolyte for solid oxide fuel cells

In this study, the quaternary solid solutions of (Bi₂O₃)_(0.8?x)(Tb₄O₇)_0.1(Ho₂O₃)_0.1(Dy₂O₃)_x (x = 0.05, 0.10, 0.15, 0.20) as an electrolyte were synthesized for solid oxide fuel cells by the technique of solid-state synthesis.

The products were characterized by X-ray powder diffraction, differential thermal analysis/thermal gravimetry and the four-point probe technique (4PPT). The total electrical conductivity is measured on the temperature and the doped concentration by 4PPT.

All samples have been obtained as the δ-phase. According to the measurements of the 4PPT, the electrical conductivities of the samples increase with the temperature but decrease with the amount of doping rate. The value of the highest conductivity (σ) is found as 1.02?×?10^?1 S cm^?1 for the system of (Bi₂O₃)_0.75(Tb₄O₇)_0.1(Ho₂O₃)_0.1(Dy₂O₃)_0.05 at 850 °C. The thermal gravimetry (TG) curve shows that there is no mass loss of sample during the measurement. The analyses of differential thermal reveal that there are neither endothermic peaks nor exothermic peaks during the heating and cooling cycles (ranging from 30 to 1000 °C).     

Fractional electrical model for modified bismuth oxide

Modified bismuth oxide (Bi₂O₃) is of great importance to fuel cells and oxide varistors. The electrical parameters of Bi₂O₃ vary with its modifying components as well as with its aging temperature. This paper presents an analysis of impedance test results carried out to find an equivalent electric model and the relationship between the model's elements to various additives used to modify Bi₂O₃ and to changes in aging temperature. The proposed model was tested via computer simulation and the model parameters correlated to individual modifiers.     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

The influence of oxidation temperature on structural, optical and electrical properties of thermally oxidized bismuth oxide films

Monoclinic bismuth oxide (Bi₂O₃) films have been prepared by thermal oxidation of vacuum evaporated bismuth thin films onto the glass substrates. In order to obtain the single phase Bi₂O₃, the oxidation temperature was varied in the range of 423-573 K by an interval of 50 K. The as-deposited bismuth and oxidized Bi₂O₃ films were characterized for their structural, surface morphological, optical and electrical properties by means of X-ray diffraction, scanning electron microscopy (SEM), optical absorption and electrical resistivity measurements, respectively. The X-ray analyses revealed the formation of polycrystalline mixed phases of Bi₂O₃ (monoclinic, α-Bi₂O₃ and tetragonal, β-Bi₂O₃) at oxidation temperatures up to 523 K, while at an oxidation temperature of 573 K, a single-phase monoclinic α-Bi₂O₃ was formed. From SEM images, it was observed that of as-deposited Bi films consisted of the well-defined isolated crystals of different shapes while after thermal oxidation the smaller dispersed grains were found to be merged to form bigger grains. The changes in the optical properties of Bi₂O₃ films obtained by thermal oxidation at various temperatures were studied from optical absorption spectra. The electrical resistivity measurement depicted semiconducting nature of Bi₂O₃ with high electrical resistivity at room temperature.     

An application of oxide and silver electrode on the BaO-doped Bi2O3 electrolyte

Oxide and silver paste were applied on the BaO-doped Bi₂O₃ electrolyte and their behavior was studied as a function of temperature and oxygen partial pressure. Interface resistance of most oxide/electrolyte were of the same order of magnitude with those of Ag paste/electrolyte in air (300–500°C). A high electrode capacitance of (0.8–1.7)×10^?2 F/cm² was observed for the silver electrode at 450°C in the P_O2 region of 1–10^?5 atm.     

Thermally stimulated luminescence of bismuth germanate ceramics with the benitoite,eulitine, and sillenite structures

Thermally stimulated luminescence (TSL) of Bi₂Ge₃O₉, Bi₄Ge₃O₁₂, and Bi₁₂GeO₂₀ and the primary components Bi₂O₃ and GeO₂ was studied under x-ray excitation. Thermal activation energies and frequency factors of trapping centers in the studied ceramics were determined. The relationships of TSL bands of the studied ceramics with maxima at 141–145 and 166–170 K and damage to the Ge sublattice and of TSL bands with maxima at 104–110 and 180–190 K and recombination processes in the Bi sublattice were demonstrated. Recombination processes causing luminescence upon nonequilibrium charge carrier release from trapping centers occur in structural complexes of similar configuration that contain the Bi ion in a nearest environment of O atoms. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 359–364, May–June, 2008.     

Structure and conductivity characterization of new type ionic conductor stabilized bismuth oxide ternary systems

In this study, the new type electrolyte (Yb₂O₃)_x(Dy₂O₃)_y(Bi₂O₃)_1-x-y ternary compounds were synthesized with different stoichiometric ratios by the solid-state reaction method at different annealing treatment and also their microstructural and electrical properties were analysed. X-ray powder diffraction results showed that the high temperature δ-phase of pure monoclinic Bi₂O₃ has been synthesized by doping of Yb₂O₃. Grain size and grain form of pellet formed samples was compared from their surface images taken by the scanning electron microscopy. The grain size has been varying between ～17–37 µm, and degrading with the increasing dopant concentrations. The relationships between the structural parameters (e.g. lattice parameters, crystallite size and the lattice microstrain) and structural properties (e.g. ionic radii of dopant cations and heat treatment procedure) were particularly discussed. Total conductivity values were calculated by Nyquistic complex impedance plot. Impedance measurement revelaed that total conductivity values of the samples increase with the increasing Yb dopant ratio. The activation energies calculated by the Arrhenius approach are measured at around 1?eV. In addition, activation energies and pre-exponential terms decrease with the increasing Yb cation dopant rate for the same ambient temperature.     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

Characteristics of X‐ray attenuation in electrospun bismuth oxide/polylactic acid nanofibre mats

The characteristics of the X‐ray attenuation in electrospun nano(n)‐ and micro(m)‐Bi₂O₃/polylactic acid (PLA) nanofibre mats with different Bi₂O₃ loadings were compared as a function of energy using mammography (i.e. tube voltages of 22–49 kV) and X‐ray absorption spectroscopy (XAS) (7–20 keV). Results indicate that X‐ray attenuation by electrospun n‐Bi₂O₃/PLA nanofibre mats is distinctly higher than that of m‐Bi₂O₃/PLA nanofibre mats at all energies investigated. In addition, with increasing filler loading (n‐Bi₂O₃ or m‐Bi₂O₃), the porosity of the nanofibre mats decreased, thus increasing the X‐ray attenuation, except for the sample containing 38 wt% Bi₂O₃ (the highest loading in the present study). The latter showed higher porosity, with some beads formed, thus resulting in a sudden decrease in the X‐ray attenuation.     

Thermostimulated surface autosegregation in bismuth ferrite single crystals

The chemical and phase composition and morphological features of the surface nanostructure have been studied by the methods of high-resolution scanning electron microscopy, X-ray microprobe analysis, and atomic force microscopy in bismuth ferrite single crystals. This structure was formed as a result of the thermostimulated surface segregation after annealing in air or vacuum at the pressure of 10⁻⁴ Pa. It has been experimentally found that, at temperatures less than 500°C, Bi₂F₄O₉ nanoparticles were formed due to the selective diffusion of iron atoms to the surface. Starting from 300°C in vacuum and 450°C in air, the segregating atom type changed and nanophases with high bismuth concentration (sillenites Bi_{26 − x} Fe _x O₃₉ and Bi₂O₃ appeared in some regions. The partial orientation of new phases has been observed in some surface regions. A probable mechanism of the described phenomenon that represents a combination of selective intrinsic mass-transport of atoms from the bulk to the surface and their thermal evaporation has been discussed.     

Formation of highly textured (1 1 1) Bi2O3 films by anodization of electrodeposited bismuth films

Highly textured bismuth oxide (Bi₂O₃) thin films have been prepared using anodic oxidation of electrodeposited bismuth films onto stainless steel substrates. The Bi₂O₃ films were uniform and adherent to substrate. The Bi₂O₃ films were characterized for their structural and electrical properties by means of X-ray diffraction (XRD), electrical resistivity and dielectric measurement techniques. The X-ray diffraction pattern showed that Bi₂O₃ films are highly textured along (1 1 1) plane. The room temperature electrical resistivity of the Bi₂O₃ films was 10⁵ Ω cm. Dielectric measurement revealed normal oxide behavior with frequency.     

非晶钛酸铋的晶化过程

利用差热分析、X射线衍射和透射电子显微镜等技术对溶胶-凝胶法合成的凝胶的晶化过程进行了分析，实验结果表明，Bi₄Ti₃O₁₂非晶凝胶晶化过程经历了四个过程：首先在433℃先形成了Bi₂O₃和TiO₂亚稳相，然后在488℃时TiO₂亚稳相与Bi₂O₃反应形成Bi，Ti复合氧化物亚稳相Bi₂T 关键词： 钛酸铋 铁电材料 溶胶凝胶 非晶 晶化过程     

Ferroelectric properties of Pr6O11-doped Bi4Ti3O12

Praseodymium doped Bi₄Ti₃O₁₂ (BIT) ceramics with composition Bi_2.9Pr_0.9Ti₃O₁₂ (BPT) were prepared by solid state reaction. These samples have polycrystalline Bi-layered perovskite structure without preferred orientation, and consist of well-developed plate-like grains with random orientation. Pr doping into BIT causes a large shift of the Curie temperature (T_C) of the BIT from 675 to 398 °C. At an electric field of 87 kV/cm, the remanent polarization and the coercive field of the BPT ceramics are 30 μC/cm² and 52 kV/cm, respectively. Furthermore, the dielectric permittivity and the dissipation factor of the BPT ceramics are 300 and 0.003 at 1 MHz, 1 V, and room temperature. Ferroelectric properties of the BPT ceramics are superior to V-doped Bi₄Ti₃O₁₂ (∼20 μC/cm² and 80 kV/cm) and (Sr, Ta)-doped Bi₄Ti₃O₁₂ (∼12 μC/cm² and 71 kV/cm) ceramics. In addition, the dense ceramics of praseodymium-doped B₄Ti₃O₁₂ were obtained by sintering at 1100 °C, about 100-200 °C lower than those of the SrBi₂Ta₂O₉ system.     

Discharged generator of singlet oxygen for oxygen-iodine laser. Transport kinetics of O2(a 1δg) and O2(b 1σ g + ) molecules and O(3 P) atoms in Ar:O2 and He:O2 flows excited by a 13.56-MHz discharge

To understand and reveal the basic physical factors providing the possibility of scaling of a discharged singlet oxygen generator (DSOG) in an oxygen-iodine laser, the production, and transport kinetics of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, as well as O(³ P) atoms, were investigated in Ar:O₂ and He:O₂ gas flows excited by a 13.56-MHz discharge in a wide range of pressures (4–40 Torr) and oxygen percentages. It is shown that the densities and transport kinetics of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) appear similar for oxygen mixtures with argon and helium in the same conditions independent of discharge mode. Compared to pure O₂, the dilution of oxygen with an inert gas allows higher energy inputs per an oxygen molecule to achieved, especially under conditions of the homogeneous discharge mode (α-mode), which gives a higher efficiency of O₂(a ¹δ_g) excitation in Ar:O₂ and He:O₂ mixtures. But the maximum attainable yield of singlet oxygen in Ar:O₂ and He:O₂ at fixed partial O₂ pressure is found to be comparable with the O₂(a ¹δ_g) yield in pure oxygen at the same pressure. The reason for this is the increased three-body deactivation of O₂(a ¹δ_g) by atomic oxygen in the mixtures because of the greater total pressure. The estimation of the rate constant of O₂(a ¹δ_g) three-body quenching by O(³ P) in Ar:O₂ and He:O₂ mixtures as (1.5 ± 0.5) × 10^?32 cm⁶/s was carried out from the analysis of transport kinetics of singlet and atomic oxygen in the discharge afterglow at high pressures exceeding ～10 Torr. A similar analysis for the lower pressures has revealed that losses both of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, and of O(³ P) atoms on the surface of the discharge tube, are determined by the density of each of the components. The obtained loss probabilities of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) on the silica surface show that the surface loss probabilities of all the species can increase noticeably under the discharge exposure. Thus, the key parameters determining the maximal O₂(a ¹δ_g) yield in the DSOG are a homogeneous volumetric mode of the discharge, energy input per oxygen molecule in this mode, and a low rate of O₂(a ¹δ_g) quenching. Just three-body quenching of O₂(a ¹δ_g) by O(³ P) limits the singlet oxygen yield with increasing pressure. The fast removal of atomic oxygen both in discharge and in the earlier afterglow could provide DSOG scaling with pressure.     

Local Trapping Centers in the Ceramics of Eulytines

Thermally stimulated luminescence (TSL) of ceramics having the structure of eulytine Bi₄X₃O₁₂ (X = Si, Ge, Zr) on exposure to x-ray irradiation in the temperature region 80–400 K is studied. An analysis of the forms of the TSL curves implies that the recombination processes in the TSL peaks at 149 and 212 K in Bi₄Si₃O₁₂ ceramics and at 143 and 230 K in Bi₄Ge₃O₁₂ ceramics can be described by the linear kinetics. The spectral composition of TSL of the ceramics obtained is investigated, and the activation energy and frequency factors which correspond to the TSL maxima are determined by various methods. Based on common spectral and energy characteristics of TSL, a conclusion concerning the connection of TSL with recombination processes in common structural complexes of BiO₆ ^9– is drawn.