Preparation and ionic conduction of CaZr1−xScxO3−α ceramics

A series of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) perovskite oxide ceramics were successfully fabricated at 1400 °C for 10 h and then further sintered at 1650 °C for 10 h via a solid-state reaction sintering process. Conductivities of the ceramics were measured under the atmosphere that contains 1% H₂/Ar and 5.63 kPa H₂O/Ar by the electrochemical impedance spectra technique. It was found that the conductivities of CaZr_1−xSc_xO_3−α (x=0, 0.05, 0.10, 0.15) ceramics increased with the increase of the measuring temperature, and the conductivity achieved its maximum value of 2.03×10⁻⁵–6.5×10⁻³ S cm⁻¹ when the doping amount of Sc (x) was 0.10. Additionally, element doping can increase the conductivities and decrease the conductivity activation energies of CaZr_1−xSc_xO_3−α ceramics. The results of transport number measurement indicated that the CaZr_0.9Sc_0.1O_3−α is almost a pure protonic conductor at 500–750 °C, while it is a mixed protonic-oxygen ionic-electronic conductor at 750–1300 °C.     

Perovskite forming ceramics of the system SrxLa1−x TiIVx+yCoIIyCoIII1−x−2yO3 for NTC thermistor applications

The paper reports the preparation, structure and electrical properties of oxide ceramic semiconductors based on the series Sr_xLa_1−x Ti^IV_x+yCo^II_yCo^III_1−x−2yO₃ with perovskite type stucture: 0<x<1, 0<y<(1−x)/2. The study starts from LaCoO₃ which is highly conductive yielding metallic condutivity above 330°C. The upset trigonal distortion of LaCoO₃ is reduced when Sr^II/Ti^IV is substituted for La^III/Co^III corresponding to increasing values of x and also when 2 Co^III are introduced for Ti^IV/Co^II into the lattice corresponding to increasing values of y. At high values of x and y othorhombic distortion occurs. At the same time, the interaction between the Co^III atoms of LaCoO₃ is increasingly interrupted providing increasing values of the the resistivity value ρ_25°C and of the B_25/100°C value deduced from measurements at 25 and 100°C according to ρ(T )=ρ_25°C e^B/T. The range of variation of x an y makes possible to prepare ceramics with desired electrical properties within the limits of ρ_25°C=1.1 Ωcm, B=1910 K and ρ_25°C=1 bis 8×10⁶ Ωcm at B-values up to 6500 K. Dependent on composition, NTC ceramics for thermistor or insurance applications are accessible. Thermistors do not show aging even at higher temperature, e.g. at 500°C, provided the single phase state is achieved as a result of mixed oxide preparation and sintering. Hence, high temperature thermistor applications are also made possible. The semiconductor behavior can be understood using the conventional polaron state hopping model.     

Dielectric properties of compositionally graded Ba1−xLaxTi1−x/4O3 thick films

Compositionally graded thick films based on lanthanum-substituted barium titanate solid solutions Ba_1−xLa_xTi_1−x/4O₃ (BLT, x=0.02, 0.04, 0.06) are prepared by tape casting and their phase structures, surface morphologies, dielectric and tunability properties have been examined. Compared with single-layered BLT film, compositionally graded BLT02/04/06 film with three-layered sandwich-structure has better temperature stability in dielectric and tunability properties. Curie peak is broadened, dielectric loss is reduced, and more importantly, it has moderate permittivity and high tunability (>35%) in a temperature range of 25–75 °C, which is beneficial for practical applications of tunable devices.     

Optical modulation and magnetic transition in PbTi1−xPdxO3−δ ferroelectric thin films

The PbTi_1−xPd_xO_3−δ (xPTPO) thin films prepared by chemical solution deposition have been investigated by means of structural characterizations, optical and magnetic measurements. X-ray diffraction patterns show that all the films have a pseudotetragonal perovskite structure, but also exhibit a lattice dilatation behavior and increased internal strain as the x increases. A possible mechanism for strain-induced structural evolution is discussed. Raman scattering further corroborates this change in average structure, where the characteristic variation of phonon modes, indirectly reveal the incorporation of Pd²⁺ ions into host lattice. Transmittance spectra analysis indicates that Pd doping has a key effect on the energy band structure. The optical bandgap of xPTPO films decreases significantly with increasing Pd content, expressed by (3.5–9.0x) eV (0≤x≤0.09). Also, magnetic switching driven by doping has been confirmed in the films, which is attributed to the competition between ferromagnetic and paramagnetic/antiferromagnetic components.     

Preparation of Bi1−xSbx films by electrodeposition

A method has been developed to produce composition modulated Bi_1–x Sb _x alloys by electrodeposition. The electrolyte which consists of NaCl 4 M and HCl 1 M (pH 0) in aqueous medium, allows codeposition of bismuth and antimony to be accomplished at room temperature on glassy carbon. The composition of the films, their crystal structure, morphology and resistivity were studied as a function of electrochemical parameters and bath composition. It is shown that the electrodeposits are monophasic and exhibit a polycrystalline state. The obtained alloys represent a continuous series of solid solution. The film composition is dependent on the applied current density. The electrical resistivity is of the order of 3–7 m.     

The relationship between the micro-mechanism and macroscopic dielectric properties in Ba1−xBixTi1−x−yZn0.75xW0.25x+yO3+y systems

A novel lead-free, high dielectric constant, ultra-wide temperature stable dielectric ceramic Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y (0.22≤x≤0.30, y=0.015) was synthesized by the traditional solid-state reaction method. The phase composition, electric and dielectric properties of the Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO₃ ceramics were investigated. The P-V-L dielectric theory was introduced. And, the chemical bond energy was calculated to track the changes in micro-structure. The relationships between chemical bond energy and the macroscopic dielectric properties(ε_r, dielectric stability and dielectric loss) in Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramics were discussed systematically. Owing to the inhomogeneous micro-structure and the diffusion in phase transition, Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramics showed a stable permittivity (~800±15%) over a ultra-wide temperature range (−30 to 375 °C). Moreover, dielectric loss was less than 0.02 and the insulation resistance was over 10¹² Ω cm. These features suggested that the Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramic could be considered as a promising candidate material for energy storage applications in harsh environment.     

Visible-light-responsive photocatalysts xBiOBr–(1−x)BiOI

A new class of oxyhalide photocatalysts xBiOBr–(1−x)BiOI prepared by a soft chemical method were characterized by X-ray diffraction and UV–Vis diffuse reflectance spectra. They are all visible-light-responsive materials with the bandgaps ranging from 1.92 to 2.91 eV. Methyl orange (MO) photocatalytic degradation experiments showed that BiOBr possessed a higher photocatalytic activity than P25 (TiO₂) under UV illumination and iodine-modified BiOBr exhibited high photocatlytic activities under visible-light irradiation. The high photocatalytic activity is in close relation with the deep valance band edge position and the internal electric fields between [Bi₂O₂] slabs and halogen anionic slabs.     

Spinel precipitation in Sn4+-doped Co1−xO polycrystals with dispersed Co2+xSn1−xO4 particles

Co_1?xO–SnO₂ powders in molar ratio of 92:8 were reactively sintered at 1400 °C to form Co_1?xO–Co_2+xSn_1?xO₄ composite and then cooled in furnace or air quenched for secondary Co_2+xSn_1?xO₄ spinel precipitation from the Sn⁴⁺ doped Co_1?xO grains. Electron microscope observations indicated the secondary spinel to precipitate at grain boundaries when slowly cooled, but as parallel-epitaxial platelets within the Sn⁴⁺ doped Co_1?xO grains with a precipitate free zone near the grain boundary when air quenched. A process of thermal-mismatch induced {1 1 0} cleaving, taking advantage of cobalt vacancies, and spontaneous healing by oxidation precipitation accounts for the platy spinel precipitation within the grains. The precipitate free zone can be attributed to cobalt vacancy depletion, i.e. site saturation, near the grain boundary during rapid cooling in air. The spinel nanocrystals nucleated from cobalt vacancies in association with Sn⁴⁺ dopant have well-developed {1 1 1} habit plane in order to minimize the coherency strain energy.     

Microstructure and characterization of Ag1−xLixNbO3 ceramics

Silver–lithium niobate, Ag_1−xLi_xNbO₃, is a promising candidate for lead-free piezoelectrics. Ceramic samples for x equal 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.08 and 0.1 were synthesized by solid state reaction. Room temperature X-ray studies indicate that all samples consist mainly of perovskite phase. Only small amounts of secondary phases, namely Ag₂Nb₄O₁₁, Ag and LiNbO₃, appear. For x≈0.06 the orthorhombic–rhombohedral morphotropic phase boundary is observed. Excellent piezoelectric properties, recently reported for x>0.1, may be the result of proximity of morphotropic phase boundary. Scanning electron microscopy and secondary ion mass spectroscopy investigations suggest that the secondary phases occur chiefly at the grain boundaries. Dielectric measurements, carried out in a wide temperature range, revealed that Ag_1−xLi_xNbO₃, for x≤0.05, undergoes the same complex sequence of phase transitions as AgNbO₃. On the other hand, for x>0.06, the temperature dependence of dielectric permittivity exhibits only two maxima, related to transitions from the ferroelectric R phase to the antiferroelectric M phase and followed by the paraelectric O phase. The dielectric results obtained confirm the existence of the morphotropic phase boundary.     

Ketonization of fatty methyl esters over Sn−Ce−Rh−O catalyst

A mixture of methyl esters of fatty acids obtained by transterification of nonerucic rape oil was ketonized. The starting material, diluted with methanol, was converted at atmospheric pressure over a catalyst that contained Sn, Ce, and Rh oxides in a molar ratio of 90:9:1. At a temperature of 385°C ketones were obtained with a total yield of 63% at the 96% conversion of starting material. The reported experiments prove that catalysts other than iron that are active in ketonization of primary alcohols can be successfully used in ketonization of esters of fatty acids. The kind of diluent used plays a crucial role in the conversion.     

Study of Water–Gas-Shift Reaction over La(1−y)SryNixCo(1−x)O3 Perovskite as Precursors

The performance of La_(1?y)Sr_yNi_xCo_(1?x)O₃ perovskites for the water gas shift reaction (WGSR) was investigated. The samples were prepared by the co- precipitation method and were performed by the BET method, XRD, TPR, and XPS. The catalytic tests were performed at 300 and 400 °C and H₂O_v/CO = 2.3/1 (molar ratio). The sample with the highest surface area is La_0.70Sr_0.30NiO₃. The XRD results showed the formation of perovskite structure for all samples, and the La_0.70Sr_0.30NiO₃ sample also presented peaks corresponding to La₂NiO₄ and NiO, indicating that the solubility limit of Sr in the perovskite lattice was surpassed. The replacement of Co by Ni favored the reduction of the species at lower temperatures, and the sample containing Sr presented the highest amount of reducible species, as identified by TPR results. All samples were active, the Sr containing perovskite appearing the most active due to the highest surface area, presence of the La₂NiO₄ phase, and higher content of Cu in the surface, as detected by XPS. Among the samples containing Co, the most active one was that with x = 0.70 (60% of CO conversion).     

SrCo1−xSbxO3−δ cathode materials prepared by Pechini method for solid oxide fuel cell applications

In this study, SrCo_1?ySb_yO_3?δ powders were prepared by a modified Pechini method. According to the study results, the cubic Pm3m phase of the SrCo_1?ySb_yO_3?δ ceramics was obtained as 10% of cobalt ions were substituted by antimony ions. Doping of Sb³⁺ ions appeared both to stabilize the Pm3m phase of the SrCo_1?ySb_yO_3?δ ceramics and to enhance densification and retard grain growth. The coefficient of thermal expansion of the SrCo_1?xSb_xO_3?δ ceramics increased with the content of the antimony ions, ranging from 10.17 to 15.37 ppm/°C at temperatures lower than the inflection point (ranging from 450 °C to 550 °C) and from 22.16 to 29.29 ppm/°C at higher temperatures. For the SrCo_0.98Sb_0.02O_3?δ ceramic, electrical conductivity reached a maximum of 507 S/cm at 450 °C. The ohmic and polarization resistances of the single cell with the pure SrCo_0.98Sb_0.02O_3?δ cathode at 700 °C read respectively 0.298 Ω cm² and 0.560 Ω cm². The single cell with the SrCo_0.98Sb_0.02O_3?δ-SDC composite cathode appeared to reduce the impedances with the R₀ and R_P at 700 °C reading respectively 0.109 Ω cm² and 0.127 Ω cm². Without microstructure optimization and measured at 700 °C, the single cells with the pure SrCo_0.98Sb_0.02O_3?δ cathode and the SrCo_0.98Sb_0.02O_3?δ-SDC composite cathode, demonstrated maximum power densities of 0.100 W/cm² and 0.487 W/cm². Apparently, SrCo_1?ySb_yO_3?δ is a potential cathode for use in IT-SOFCs.     

热处理对锌−镍−磷−纳米二氧化硅复合电镀层性能的影响

先采用由110 g/L ZnCl_2、100 g/L NiCl_2·6H_2O、80 g/L CH_3COONH_4、40 g/L CH_3COONa、5～10g/L NaH_2PO_2·H_2O、180 g/L KCl、0.04～0.08 g/L十二烷基硫酸钠和4～6 g/L纳米SiO_2 (平均粒径7～40 nm)组成的镀液,在pH为4～5、温度为45℃和电流密度为1.5 A/dm2的条件下电镀20 min得到厚度为30～40μm的Zn-Ni-P-纳米SiO_2复合镀层。然后在氮气保护和不同温度(200、300、400和500℃)下热处理2 h。研究了热处理温度对复合镀层微观结构、显微硬度和耐蚀性的影响。结果表明,经300℃热处理的Zn-Ni-纳米SiO_2复合镀层的综合性能较好,显微硬度为198 HV,耐蚀性最好。     

Catalytic properties of SrSn1−xSbxO3 in methanol oxidation

Ceramic model catalyst materials of general formula SrSn_1–x Sb _x O₃ are synthesised by solid state reaction. X-ray diffraction shows the materials to be single phase over the composition range 0 x0.085, with a second phase, identified as SrSb₂O₅, being produced at higher antimony doping levels. XPS, Auger electron spectroscopy and valence band photoemission show strong segregation of Sb to the surface of the material even within the single phase regime. The catalytic properties of the materials are examined using methanol oxidation as a test reaction. The activity and selectivity to formaldehyde production shown by these materials is found to be strongly correlated with the attainment of the bulk solubility limit of Sb in the SrSnO₃ perovskite host.     

Layered perovskite structured La5−xSrxTi4+xSc1−xO17 microwave ceramics for dielectrically loaded antennas

The crystal structure, microstructure and dielectric properties of layered perovskite structured La_5−xSr_xTi_4+xSc_1−xO₁₇ (x=0–0.8) ceramics prepared by a solid state reaction route were investigated. X-ray diffraction and Raman spectroscopy analysis revealed the formation of single phase orthorhombic (Pnnm) symmetry. The microwave dielectric properties (ε_r, Q×f_o and τ_f) of samples have been investigated as a function of composition. ε_r and τ_f increased while Q×f_o decreased with an increase in x. The sample x=0.6 exhibited ε_r=54.8, Q×f_o= 12,260 GHz and τ_f=6.7 ppm/°C which may be a suitable candidate material for dielectrically loaded antenna applications. The complex impedance spectroscopy analysis of the sample x=0.6 revealed that the sample is highly insulative with two electro-active regions (bulk and grain boundary).     

Nonstoichiometry in perovskite-type oxide Ca1−x Ce x MnO3−δ and its properties in alkaline solution

Nonstoichiometry in high conductivity perovskite-type oxide Ca_1-x Ce _x MnO_3- was investigated. At room temperature in air, the 3- value was determined to be 2.91 for CaMnO_3-, which meant that 82% of manganese was tetravalent. Although the 3- value increased by increasing the cerium content, i.e. by doping of higher valent cation into the calcium site, the quantity of Mn⁴⁺ in the sample oxide essentially decreased with increasingx. The oxygen contents change reversibly with temperature in air. Change of oxygen content was also observed on discharging this oxide as the cathode material of a battery in alkaline solution. Surprisingly, the sintered ceramics of this oxide worked as a cathode without mixing with a conductive powder such as graphite. Considering the discharging performance, this oxide may be a candidate for the cathode material of the alkaline battery.