Yttria-stabilized zirconia thin films with restrained columnar grains for oxygen ion conducting electrolytes

Yttria-stabilized zirconia thin films with restrained columnar grains were deposited by modifying the DC reactive magnetron sputtering conditions. Usually, films fabricated by physical vapor deposition (PVD) method generate columnar grain structures due to its deposition characteristics. The grain boundaries between these columnar grains can be considered as structural defects and causes serious issues for the application of thin film electrolyte of energy conversion systems. By modifying the background pressure and deposition temperature of the reactive sputtering method, YSZ thin films having restrained columnar grains were successfully fabricated. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations were conducted to analyze the surface morphologies, grain structures, and nano-defects in the interior of the YSZ thin film. Through the analysis, restrained columnar microstructures of the YSZ films were deposited as dense and homogeneous. The film also showed higher ionic conductivity compared to that of the columnar structure due to the reduced ion transport blocking effect. Moreover, the fuel cell fabricated with the YSZ electrolyte having restrained columnar grains showed superior performance in terms of the peak power density than the fuel cell with columnar grain electrolyte structure.     

电化学沉积法制备钇稳定ZrO2(YSZ)薄膜

引　言钇稳定二氧化锆 (ＹＳＺ)是制备氧化物燃料电池和氧传感器的重要材料 .电解质薄膜化是开发高输出电流密度的固体氧化物燃料电池和高灵敏度的传感器的研究方向 .电化学气相沉积 (ＥＶＤ) [1～ 3] 制得的薄膜致密 ,且厚度仅 2 0～ 4 0 μｍ ,薄膜性能优良 ,但设备复杂 ,制备成本高 ,反应生成的氯气腐蚀性大 .激光沉积法具有设备复杂、成本高等问题 .等离子喷涂 (ＶＰＳ、ＡＰＳ) [4 ,5] 适于大规模制膜 ,但薄膜不够致密 ,裂缝较多 .溶胶 -凝胶法 (Ｓｏｌ -Ｇｅｌ) [4 ,6 ,7] 制得的ＹＳＺ薄膜致密且薄 ,设备简单 ,但对于基片要求很严 ,…     

Doping-level control of atomic layer deposited YSZ surface layer on platinum catalyst

While local surface composition of fuel cell electrode is critical to performance, precise control of the surface composition at the thickness scale of <10 nm has been challenging. Here we report on the fabrication of ultra-thin (5 nm-thick) yttria-stabilized zirconia (YSZ) surface layers whose compositions are precisely controlled by using atomic layer deposition (ALD), and their applications to cathodic overlayers of low-temperature solid oxide fuel cells. Exchange current density was improved by 80% by optimizing the doping level (16 mol%) of YSZ overlayer. Activation resistance of the cell with 16 mol% doped ALD YSZ overlayer decreased by 27%, and the cell performance improved by 70% compared to the cell without the overlayer. Such improvement was attributed to the ability of the doping-controlled ALD YSZ overlayer to locally improve O^2? incorporation, which is the rate-determining step of oxygen reduction reaction, at the cathode surface.     

The influence of thermal barrier coating dissolution on CMAS melt viscosities

Glassy deposits, largely consisting of CaO-MgO-Al₂O₃-SiO₂ (CMAS), are a common product on thermal barrier coatings (TBCs) within gas-turbines after an interaction with airborne particles. Here, in order to facilitate the quantification and modelling of the spreading and infiltration behavior of CMAS melts onto and into TBCs we have determined the high temperature viscosities of four widely used synthetic “CMAS” melts and the influence of TBC materials (yttria-stabilized zirconia (YSZ) and gadolinium zirconate (GZO)) dissolution upon them. After a dissolution of 6.5 wt% YSZ or GZO one out of four CMAS melts shows no significant change in viscosity, while the other three melts exhibit a viscosity increase at lower temperatures that continuously changes to a decrease in viscosity towards higher temperatures. The influence of the doping amount on the viscosity was investigated in detail for one CMAS melt (C₃₅M₁₀A₇S₄₈) and parametrized.     

Optical properties of gadolinia-doped cubic yttria stabilized zirconia single crystals

Cubic zirconia single crystals stabilized with yttria and doped with Gd₂O₃ (0.10–5.00 mol%) were prepared by the optical floating zone method, and characterized by a combination of X-ray diffraction (XRD), and Raman, electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis), photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopic techniques. XRD and Raman spectroscopy showed that the crystal samples were all in the cubic phase, whereas the ceramic sample consisted of a mixture of monoclinic and cubic phases. The absorption spectrum showed four peaks at 245, 273, 308, and 314 nm in the ultraviolet region, and the optical band gap differed between samples with ≤3.00 mol% and those with >3.00 mol% Gd₂O₃. The emission spectrum showed a weak peak at 308 nm and a strong peak at 314 nm, which are attributed to the ⁶P_5/2 → ⁸S_7/2 and ⁶P_7/2 → ⁸S_7/2 transitions of Gd³⁺, respectively. The intensities of the peaks in the excitation and emission spectra increased with Gd³⁺ concentration, reached a maximum at 2.00 mol%, then decreased with higher concentrations. This quenching is considered to be the result of the electric dipole-dipole interactions, and this interpretation is supported by the Gd³⁺ EPR spectra, which showed progressive broadening with increasing Gd³⁺ concentration throughout the concentration range investigated.     

High porous yttria-stabilized zirconia with aligned pore channels: Morphology directionality influence on heat transfer

High porous yttria stabilized zirconia with unidirectionally aligned channels is used in engineering applications with extremely low thermal conductivity. This property is strongly influenced by microstructure features such as pore volume fraction, pore size distribution, random porous microstructure and pore morphology directionality. Although several models are reported in the available literature, but their analytical formulas are formalised for homogeneous structures or they are based on proportion between solid and fluid phases. These differences from real microstructures cause significant computational errors especially when thermal conductivity changes as the function of the measurement direction (parallel or perpendicular). In this context, the application of an intermingled fractal unit's procedure capable of reproducing porous microstructure as well as predicting thermal conductivity has been proposed. The results are in agreement with experimental ones measured for parallel and perpendicular directions and suggest improving the formalisation of fractal modelling in order to obtain an instrument of microstructure design.     

Yttria-stabilized zirconia closed end tubes prepared by electrophoretic deposition

The electrophoretic deposition technique was used for the preparation of ZrO₂:8 mol% Y₂O₃ (yttria-stabilized zirconia, 8YSZ) closed end tubes for application in high temperature oxygen sensing devices. The 8YSZ ceramic suspensions with different average particle sizes were investigated looking for the best conditions for electrophoretic deposition of thin wall closed end ceramic tubes. High deposition rate of the ceramic particles onto graphite were obtained with isopropanol as solvent and 4-hydroxybenzoic acid as dispersant, with good surface quality of the deposited layer. The green tubes were dried and sintered at 1500 °C, and their properties were analyzed by X-ray diffraction for determination of the structural phases, scanning probe microscopy for observation of grain morphology, and impedance spectroscopy for evaluation of the oxide ion electrical resistivity. Pt/YSZ tube/Pt electrochemical cells were assembled for exposure to oxygen in the 60-650 ppm range using an electrochemical YSZ oxygen pump and sensor system. The signal response of the electrophoretic deposited sensor was similar to the response of the sensor of the oxygen pump. Several thin wall 4 mm diameter × 30 mm length closed end tubes may be obtained in a single operation, showing the ability of this technique for processing large quantities of tubular solid electrolytes with electrical properties suitable for use in high temperature devices.     

Evolution mechanism of the microstructure and mechanical properties of plasma-sprayed yttria-stabilized hafnia thermal barrier coating at 1400 °C

Yttria stabilized hafnia (Hf_0.84Y_0.16O_1.92, YSH16) coatings were sprayed by atmospheric plasma spraying (APS). The effects of thermal aging at 1400 °C on the microstructures, mechanical properties and thermal conductivity of the coatings were studied. The results show that the as-sprayed coating was composed of the cubic phase, and the nano-sized monoclinic (M) phase was precipitated in the annealed coating. The presence of M phase effectively constrained the sintering of the coating due to its superior sintering-resistance. The Young's modulus kept at a nearly same level of ~78 GPa even after annealing, and the coating annealed for 6 h yielded a maximum value of hardness but revealed a declining tendency in the Vicker's hardness with prolonged sintering time. The thermal conductivity increased from 0.8-0.95 W m^-1 K^-1 at as-sprayed state to 1.6 W m^-1 K^-1 after annealing at 1400 °C for 96 h. The dual-phase coating is promising to serve at temperatures above 1400 °C due to its excellent thermal stability and mechanical properties.