氧化钇稳定氧化锆的制备及电性能测试

氧化钇稳定氧化锆(yttria-stabilized zirconia,YSZ)是目前使用最多的电解质材料,探索了以YSZ纳米粉体为原料,采用固相法制备YSZ电解质薄片。采用X射线衍射(XRD)测试了它的微结构;采用交流四端子法测瓷体的电导率。实验表明,最佳烧结温度在1300℃,气孔含量少、晶粒均匀,电导率高,800℃时为0.08 S.m-1,是理想的高温电解质材料。     

固体氧化物燃料电池氧化钇稳定氧化锆电解质的等离子喷涂制备及性能

金属支撑型固体氧化物燃料电池极具应用前景,但缺少高性价比制备技术。采用高效率、低成本大气等离子喷涂（APS）在金属基体上制备了氧化钇稳定氧化锆（YSZ）电解质,研究加热基体条件下沉积粒子形貌与涂层结构间的联系,并评估电解质的力学性能和电池性能。结果表明：加热后的基体上,YSZ沉积粒子铺展充分,片层内存在微裂纹,导致结构中除未结合区域外还存在垂直裂纹,涂层孔隙率为7.16%,YSZ纳米压痕硬度和弹性模量分别为（13.0±1.0） GPa和（188.5±2.6） GPa。受电解质不致密的影响,APS沉积的YSZ单电池最高开路电压为0.97 V,致密度还需进一步提高,但电池输出性能可观,900℃峰功率密度为850 mW/cm²。随着设备迭代优化或结合后处理工艺,APS有望实现致密YSZ电解质的大规模低成本制备。     

医用氧化钇稳定氧化锆陶瓷的制备及成型工艺

氧化钇稳定氧化锆陶瓷(Y-TZP)与其他稳定类型的氧化锆陶瓷相比,具有烧结温度低、高硬度、断裂韧性和抗弯强度以及良好的生物相容性等优点,因此成为目前最理想的齿科修复材料之一。但是氧化钇稳定氧化锆陶瓷的高硬度、高强度也给牙科修复材料的制造工艺带来了一定的困难。总结了氧化钇稳定的氧化锆陶瓷的制备方法和成型工艺,指出了不同制备方法和成型工艺的优点和不足,并对医用氧化锆陶瓷未来的发展趋势提出了展望。     

两步烧结法制备纳米氧化钇稳定的四方氧化锆陶瓷

采用共沉淀法制备纳米氧化钇稳定的四方氧化锆（yttria stabilized tetragonal zirconia,3Y-TZP）粉体。利用X射线衍射、N2吸附–脱附等温线,透射电子显微镜对3Y-TZP粉体的物理性能和化学性能进行表征。研究了纳米3Y-TZP粉体的烧结曲线,分析了3Y-TZP素坯在烧结过程中的致密化行为和显微结构,探讨了两步烧结工艺对3Y-TZP纳米陶瓷微观结构的影响。结果表明：采用共沉淀法,在600℃煅烧2h后,可获得晶粒尺寸为13nm、晶型发育良好、团聚较少的纳米3Y-TZP粉体;采用两步烧结法,将素坯升温至1200℃保温1min后,再降温到1050℃保温35h,可获得相对密度大于98%,晶粒尺寸约为100nm的3Y-TZP陶瓷。两步烧结法通过控制煅烧温度和保温时间,利用晶界扩散及其迁移动力学之间的差异,使晶粒生长受到抑制,样品烧结致密化得以维持,实现在晶粒无显著生长前提下完成致密化。     

亚微米晶粒氧化钇稳定氧化锆电解质的稳定性

氧化钇稳定氧化锆(yttria-stabilized zirconia,YSZ)是目前使用最多的电解质材料,YSZ结构和性能的长期稳定对固体氧化物燃料电池(solid oxide full cell,SOFC)系统的可靠性至关重要。重点研究了具有亚微米结构的YSZ在850℃环境中的长期老化性能,结果发现:在850℃空气气氛中老化处理300h后,YSZ中小于1μm的部分晶粒出现了继续生长的现象,使得小于1μm晶粒比例下降10%～20%;当这部分晶粒长大到1～2μm,呈现稳定状态,即没有出现晶粒的过分长大;老化600h和1000h后,小晶粒(小于1μm)所占比例几乎不变。伴随着晶粒尺寸分布变化,YSZ电解质的电导率也比老化处理初期(300h)有所降低;当老化处理600h后,电导率下降趋势变缓;老化处理1000h后,电导率基本稳定,且1000℃电导率仍然保持在0.15S/cm以上。电导率下降主要是由YSZ晶粒部分长大引起的。具有上述性能的YSZ用作SOFC电解质可以满足长期使用的要求。     

三维有序大孔氧化钇稳定氧化锆的制备与表征

以聚苯乙烯(polystyrene, PS)胶体晶体为模板,采用柠檬酸凝胶方法制备氧化钇稳定氧化锆(yttria stabilized zirconia, YSZ)前驱体溶胶,采用浸渍-提拉方法向PS模板的空隙中填充YSZ溶胶,煅烧去除模板后成功地制备了三维有序大孔YSZ材料.研究前驱体溶胶不同浓度、浸渍次数以及煅烧条件等因素对大孔YSZ结构的影响.用扫描电子显微镜对YSZ的微观结构进行表征.结果表明:前驱体溶胶的浓度在0.3～0.4 mol/L的范围内,浸渍次数为1次或2次,煅烧温度为600℃时可以得到高度有序的大孔YSZ.     

氧化钇稳定氧化锆涂层的研究现状

由于氧化钇稳定氧化锆(YSZ)陶瓷材料在作为热障涂层的使用过程中存在因抗烧结性能差、应力裂纹、涂层脱落等导致涂层失效的问题,本文主要从热障涂层的制备工艺,抗烧结性能、控制TGO的生长、抗CMAS腐蚀及YSZ面层应变容限等方面的改善方法进行论述,通过提高涂层纯度、改变粘接层及涂层成分、涂层结构及制备柱状结构YSZ陶瓷面层释放热失配应力等可有效改善涂层在使用过程中的失效问题。     

非对称LSCF中空纤维透氧膜的制备及性能

采用溶胶–凝胶法制备了具有钙钛矿型结构的La0.6Sr0.4Co1–yFeyO3–δ(LSCF,y=0.2,0.5或0.8)氧化物,然后以相转化烧结技术制备了LSCF中空纤维透氧膜,考察了凝固浴与Co/Fe摩尔比对LSCF中空纤维膜微结构及透氧性能的影响.使用70％(质量分数)NMP与30％乙醇的混合液作为内凝固浴,去...     

相转化法制备氧化钇稳定氧化锆中空纤维陶瓷膜

采用相转化和烧结相结合的方法制备了氧化钇稳定氧化锆(YSZ)中空纤维陶瓷膜，研究了铸膜液中YSZ粉末含量和烧结温度对中空纤维陶瓷膜的微观结构和性能的影响。结果表明，YSZ中空纤维陶瓷膜的不对称结构包含指状结构和海绵状结构，YSZ含量会影响两种结构的比例，烧结则会引起微观结构的致密化。在铸膜液配比为m(YSZ):m(PSF):m(NMP)=5.0:1:4，烧结温度为1200 ℃的条件下制备出性能良好的中空纤维陶瓷膜，其纯水通量为2.33 m3/(m2·h·MPa)，抗弯强度为134.5 MPa。     

等离子喷涂制备疏水氧化钇稳定氧化锆涂层及其抗垢耐蚀性研究

针对水环真空泵叶轮叶片、壳体等关键部件的结垢与腐蚀问题,采用等离子喷涂工艺和硬脂酸表面修饰的方法在Q235B基体表面制备疏水的氧化钇稳定氧化锆(YSZ)涂层。采用扫描电子显微镜、能谱仪、万能拉伸试验机、接触角测量仪等仪器和结垢试验、电化学试验等方法对涂层的微观结构及性能进行表征。结果表明,YSZ涂层表面具有“乳突”状的微纳结构,组织结构较为致密。Ni Cr Mo Fe粘结层的添加使涂层的结合强度提高了31%。硬脂酸修饰后涂层表面的平均水接触角达到141.8°,在过饱和碳酸钙溶液中浸泡后的结垢少,在3.5%NaCl溶液中的腐蚀电流密度与基体相比降低了94%,表现出良好的抗垢耐蚀性能。     

Thin Yttrium-Stabilized Zirconia Electrolyte Solid Oxide Fuel Cells by Centrifugal Casting

A centrifugal casting technique was developed for depositing thin 8-mol%-yttrium-stabilized zirconia (YSZ) electrolyte layers on porous NiO-YSZ anode substrates. After the bilayers were cosintered at 1400°C, dense pinhole-free YSZ coatings with thicknesses of ∼25 μm were obtained, while the Ni-YSZ retained porosity. After La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF)-Ce_0.9Gd_0.1O_1.95 (GDC) or La_0.8Sr_0.2MnO₃ (LSM)-YSZ cathodes were deposited, single SOFCs produced near-theoretical open-circuit voltages and power densities of ∼1 W/cm² at 800°C. Impedance spectra measured during cell tests showed that polarization resistances accounted for ∼70%–80% of the total cell resistance.     

Preparation of Dense Platinum-Yttria Stabilized Zirconia and Yttria Stabilized Zirconia Films on Porous La0.9Sr0.1MnO3 (LSM) Substrates

A sol–gel process has been developed to prepare fine powder of La_0.9Sr_0.1MnO₃ (LSM) with an average particle size ∼40 nm. The LSM powder is pressed to pellets, on which a uniform green yttria-stabilized zirconia (YSZ) film is deposited using an electrophoretic deposition process. A green composite film of platinum and YSZ (Pt-YSZ) is prepared on the top of the green YSZ film using a colloidal process, followed by filling the pores using a sol–gel process. The three-layered structure, a green Pt-YSZ film, and a green YSZ film on a green LSM substrate, is fired at 1250°C for 3 h, resulting in a dense Pt-YSZ and YSZ film supported by a porous LSM substrate. Electrical measurements show that the sensors with the three-layered structure display a well-defined diffusion-limited current in gases containing partial pressure of oxygen up to ∼9 vol%, implying that the quality of the Pt-YSZ and YSZ film is adequate for the sensor application.     

Alumina and Alumina/Zirconia Multilayer Composites Obtained by Slip Casting

The slip casting technique has been revealed as a powerful method to obtain multilayer composites close to theoretical density. From zeta potential and viscosity measurements of Al₂O₃ and Al₂O₃/ZrO₂ (4 vol% ZrO₂) suspensions, the corditions for the preparation of multilayer composites by slip casting have been determined. A microstructural analysis of the different layers by scanning electron microscopy is also reported.     

添加Li_2O对YSZ电解质性能影响

8%（摩尔分数,下同）Y2O3稳定的ZrO2（8YSZ）是固体氧化物燃料电池（SOFC）中最常用的电解质材料,本文研究了在8YSZ基体中加入n%Li2O（n=0,0.25,0.50,1.00,1.50,1.70,2.00,2.50,3.00）后（记为n%Li2OYSZ）对其晶相结构、晶格常数、烧结性能、微观形貌、电导率及其作为SOFC电解质性能的影响。结果表明,Li2O中的Li＋可以固溶到YSZ的晶格内使其晶格常数减小;Li2O的加入量n〈1.70时,瓷体在烧结过程中不会发生相变。加入少量的Li2O（n=0.25,0.50）可以提高YSZ的致密度和电导率,0.25%Li2OYSZ和0.50%Li2OYSZ样品800℃的电导率分别高达0.030 2 S/cm和0.027 6 S/cm,分别是纯YSZ的1.35和1.24倍;当Li2O含量n≥1.00时,相同条件下烧结体致密度随Li2O加入量的增大而逐渐减小;当n≥1.70时,样品在烧结过程中虽然出现相变,但在高于1400℃可以烧结致密,并得到纯立方相YSZ。将1250℃烧结制得的0.25%Li2OYSZ和0.50%Li2OYSZ作为SOFC电解质的单电池,800℃时的开路电压高于1.0V,说明YSZ中没有出现电子电导,具有比纯YSZ为电解质的单电池更高的性能输出,表现出了良好的应用前景。     

Strength and Toughness of Tape-Cast Yttria-Stabilized Zirconia

The biaxial flexural strength and fracture toughness of tape-cast yttria-stabilized zirconia, for application as the electrolyte in solid oxide fuel cells, have been measured at room temperature and at a typical operating temperature of 900°C. The flexural strength was measured in ring-on-ring loading and decreased from 416 MPa at room temperature to 265 MPa at 900°C. The fracture toughness was measured using two different techniques: indentation fracture and double-torsion loading. The latter was more reliable and gave a fracture toughness of 1.61 ± 0.12 MPa·m^1/2 at room temperature and 1.02 ± 0.05 MPa·m^1/2 at 900°C. The flexural strength and fracture toughness were quantitatively consistent with fracture being initiated at the observed surface defects. The lower fracture toughness at 900°C is partly due to a reduction in elastic modulus and partly due to a reduction in the work of fracture.     

Effect of optical basicity on the stability of yttria‐stabilized zirconia in contact with molten oxy‐fluoride flux

Solid oxide membrane (SOM) electrolysis process can produce high‐purity silicon from SiO₂ dissolved in molten oxy‐fluoride flux at elevated temperatures. Yttria‐stabilized zirconia (YSZ), the preferred material for the oxygen‐conducting membrane for this application, is found to degrade over time upon exposure to the silica‐containing molten oxy‐fluoride flux. This YSZ degradation is caused by the acidity of the dissolved silica, especially when the optical basicity of the molten flux is lower than that of the yttria present in the YSZ membrane. To counteract this mismatch, the addition of CaO, a basic oxide, to the flux can adjust the optical basicity of the flux and successfully mitigate the YSZ membrane degradation. The detailed correlation between the rate of YSZ membrane degradation and the optical basicity of the flux is investigated by systematically testing a series of flux compositions. It is found that as the oxide optical basicity in the flux approaches that of the yttria in the YSZ, the degradation of the YSZ membrane is mitigated and essentially vanishes when the flux acidity with respected to the yttria is neutralized. This approach provides a guideline for eliminating membrane degradation during the production of silicon using the SOM electrolysis process.     

Preparation of Yttria-Stabilized Zirconia Thin Films on Strontium-Doped LaMnO3 Cathode Substrates via Electrophoretic Deposition for Solid Oxide Fuel Cells

A yttria-stabilized zirconia (YSZ) thin film on an La_0.8Sr_0.2MnO₃ porous cathode substrate was prepared, using electrophoretic deposition (EPD) to fabricate a solid oxide fuel cell (SOFC). The electrical conductivity of an La_0.8Sr_0.2MnO₃ substrate is satisfactorily high at room temperature; therefore, YSZ powder could be deposited electrophoretically onto an La_0.8Sr_0.2MnO₃ substrate without any extra surface treatment, such as a metal coating. Successive repetition of EPD and sintering was required to obtain a film without gas leakage, because of the thermal expansion coefficient mismatch between the YSZ and the La_0.8Sr_0.2MnO₃ substrate. On the other hand, the electromotive force of the oxygen concentration in the cell that used YSZ film prepared via EPD increased and attained the theoretical value when the number of deposition and calcination cycles was increased. Six or more successive repetitions were required to obtain a YSZ film without gas leakage. A planar-type SOFC was fabricated, using nickel as the anode and YSZ film (∼10 μm thick) that had been deposited onto the La_0.8Sr_0.2MnO₃ substrate as the electrolyte and cathode. The cell exhibited an open circuit voltage of 1.0 V and a maximum power density of 1.5 W/cm². Thus, the EPD method could be used as a colloidal process to prepare YSZ thin-film electrolytes for SOFCs.     

Mechanism of Thermal Transport in Zirconia and Yttria-Stabilized Zirconia by Molecular-Dynamics Simulation

We present results of molecular-dynamics simulations of the thermal conductivity, κ, of ZrO₂ and Y₂O₃-stabilized ZrO₂ (YSZ). For both pure ZrO₂ and YSZ with low concentrations of Y₂O₃, we find that the high-temperature κ is typical of a crystalline solid, with the dominant mechanism being phonon-phonon scattering. With increasing Y₂O₃ concentration, however, the mechanism changes to one more typical of an amorphous system. In particular, phononlike vibrational modes with well-defined wave vectors appear only at very low frequencies. As in amorphous materials, the vast majority of vibrational modes, while delocalized, do not propagate like ordinary phonon modes but transport energy in a diffusive manner. We also find that the few highest frequency modes are localized and do not contribute to κ.