Industrial growth of yttria-stabilized cubic zirconia crystals by skull melting process

We reported the development of a Ф100 cm growth apparatus for skull melting growth of yttria-stabilized cubic zirconia(YSZ) crystals and more than 1000 kg crystals have been grown in the furnace each time.The growth conditions were optimized and the structure of the as-grown crystals was characterized by X-ray diffraction.The transmittance of 15 mol.% yttria-stabilized cubic zirconia crystal was nearly 80% in the range of 400–1600 nm.The refractive indices were measured and fitted the Sellmeier equation whi...

SURFACE ELECTRICAL PROPERTIES AND STRUCTURE OF YTTRIA-PARTIALLY-STABILIZED ZIRCONIA IMPLANTED WITH ^(57) Fe IONS

Sintered plates of 5mol% yttria-partially-stabilized zirconia have been implanted at room temperature with 5 ×1015to 2 ×1017 Fe+ ions/cm2 at 140 KeV. Electrical measurement, Rutherford backscattering spec-troscopy(RBS), Raman spectroscopy and X-ray photoelec-tron spectroscopy(XPS) have been used to study the surface electrical properties and the structure of the implanted layer before and after thermal annealing treatment in N2.

Preparation of alumina-doped yttria-stabilized zirconia nanopowders by microwave-assisted peroxyl-complex coprecipitation

Alumina-doped yttria-stabilized zirconia (ADYSZ) nanopowders were prepared by microwave-assisted peroxyl-complex coprecipitation (MAPCC) using ZrOCl2·8H2O, Y2O3 and AlCl3·6H2O as starting materials, NH3·H2O as precipitant and H2O2 as complexant. The effects of adding H2O2 and microwave drying on the preparation and properties of ADYSZ were investigated. The precursors and nanopowders were studied by EDX, XRD, SEM and TEM techniques. The results show that the uniformity of component distribution within ADYSZ nanopowders is improved by adding appropriate dosage of H2O2. Complexing reaction between H2O2 and Zr4+ ion restrains the hydrolyzation and precipitation of Zr4+ ion. With the addition of H2O2, Al3+, Y3+ and Zr4+ ions can be precipitated synchronously in a relatively narrow range of pH value. H2O2 also improves the filterability of the wet precipitate. The highly hydrophilic precipitates can be quickly and effectively separated from aqueous solution. During microwave drying process, the moisture of wet precursors is selectively heated. Quick expansion of steam vapor within the wet colloidal particles causes the aggregations burst into numerous tiny lumps. Compared with oven drying, microwave drying can not only shorten drying time but also reduce aggregation intensity of the resultant ADYSZ nanopowders.

A review of C_1 chemistry synthesis using yttrium-stabilized zirconia catalyst

C1 chemistry based on synthesis gas, methane, and carbon dioxide offers many routes to industrial chemicals. The reactions related to the synthesis of gas can be classified into direct and indirect approach for making such products, such as acetic acid, dimethyl ether, and alcohol. Catalytic syngas processing is currently done at high temperatures and pressures, conditions that could be unfavorable for the life of the catalyst. Another issue of C1 chemistry is related to the methane-initiated process. It has been known that direct methane conversions are still suffering from low yields and selectivity of products resulting in unprofitable ways to produce products, such as higher hydrocarbons, methanol, and so on. However, many experts and researchers are still trying to find the best method to overcome these barriers, for example, by finding the best catalyst to reduce the high-energy barrier of the reactions and conduct only selective catalyst-surface reactions. The appli- cation of Yttria-Stabilized Zirconia （YSZ） and its combination with other metals for catalyzing purposes are increasing. The existence of an interesting site that acts as oxygen store could be the main reason for it. Moreover, formation of intermediate species on the surface of YSZ also contributes significantly in increasing the production of some specific products. Understanding the phenomena happening inside could be necessary. In this article, the use of YSZ for some C1 chemistry reactions was discussed and reviewed.

Resistive Switching in Stabilized Zirconia Films Studied by Conductive Atomic Force Microscopy

We have applied Conductive Atomic Force Microscopy (CAFM) to study the microscopic mechanism of resistive switching in the ultrathin (3 - 5 nm) yttria stabilized zirconia (YSZ) films. Using CAFM, we were able to trace the growth of the individual conductive filaments, which are considered now to be responsible for the resistive switching effect in the transition metal oxides. The growth of the filaments has been proven to be initiated by the defects in the film material including the ones, which are the concentrators of the electric field, in particular, by the roughness (hillocks) of the film/substrate interface. The electron transport via individual filaments has been studied. Besides the butterfly-type hysteresis in the current-voltage (I-V) curves of the probe- to-sample contact typical for the bipolar resistive switching, we have observed the I-V curves with resonant peaks attributed to the resonant electron tunneling via the localized electron states in the filaments.

锆基陶瓷热障涂层的腐蚀研究进展

近年来随着航空与航海工业的迅速发展,具有耐高温、长寿命、耐腐蚀等优势的发动机叶片成为开发新一代航空发动机和涡轮发动机的重要一环。热障涂层(TBCs)作为常用的热防护技术,一方面可为发动机叶片部分金属基底提供隔热保护,使其免受高温气体的影响;但另一方面,更高的发动机工作温度使得叶片及其表面TBCs遭受严重的环境沉积物腐蚀,造成过早失效,腐蚀类型主要有热腐蚀、CMAS腐蚀、熔盐腐蚀等。腐蚀已成为限制TBCs工作温度和服役寿命的难题,抗腐蚀防护是目前TBCs领域研究的重点。本文首先简述了以氧化钇稳定氧化锆陶瓷(YSZ)为主的热障涂层材料的主要特性,再简述了TBCs的不同腐蚀的反应机理,重点从涂层的微观结构设计、梯度涂层的设计、涂层成分改性及掺杂改性等方面与涂层腐蚀过程之间的影响关系出发,阐述了TBCs改性方法与涂层腐蚀的特点。提出未来涂层改进与防护的几种方法,最后对TBCs的腐蚀防护发展方向进行了展望。

Composite ceramics thermal barrier coatings of yttria stabilized zirconia for aero-engines

Composite ceramics thermal barrier coatings(TBCs) are widely used in the aero-engines field due to their excellent thermal insulation, which improves the service life and durability of the inherent hot components. The most typical, successful and widely used TBCs material is yttria stabilized zirconia(YSZ). In this paper, fabrication methods, coating structures, materials, failure mechanism and major challenges of YSZ TBCs are introduced and reviewed. The research tendency is put forward as well. This review provides a good understanding of the YSZ TBCs and inspires researchers to discover versatile ideas to improve the TBCs systems.

Microstructure and thermal cycling behavior of nanostructured yttria partially stabilized zirconia (YSZ) thermal barrier coatings

Nanostructured yttria partially stabilized zirconia(YSZ) coatings were prepared by atmospheric plasma spraying(APS) using the conglomeration made by zirconia nanoparticle as the raw materials.The measurement methods,which consisted of scanning electron microscopy(SEM),transmission electron microscopy(TEM) and thermal cycling behavior,were used to character the morphology,composition and thermal oxidation behavior of the powder and the coatings.From the results,it was shown that the YSZ coating was the laminar structure,and the elements distribution in the bond and top coat were well-proportioned.The YSZ coatings were composed of fine grains with size ranging from 30 to 110 nm.The laminar layers with columnar grains were surrounded with unmelted parts of the nanostructured powder and some equiaxed grains.In the as-sprayed nanostructured zirconia coatings,there existed pores that were less than 1 μm.The cracks were observed on some of the crystal border.The cyclic oxidation experiment showed that the nanostructured coating had longer thermal cycling lifetime to exhibit the promising thermal cyclic oxidation resistance.The failure of the nanostructured TBC was similar to the failure of conventional APS TBC.

Densification behavior of yttria-stabilized zirconia powders for solid oxide fuel cell electrolytes

Yttria-stabilized zirconia(YSZ) is the most common electrolyte material for solid oxide fuel cells. Herein, we conducted a comparative study on the densification behavior of three different kinds of commercial 8 mol% YSZ powders:(i) TZ-8Y(Tosoh, Japan),(ii) MELox 8Y(MEL Chemicals, UK), and(iii) YSZ-HT(Huatsing Power, China). The comparison was made on both the selfsupporting pellets and thin-film electrolytes coated onto a NiO–YSZ anode support. For the pellets, MELox 8Y showed the highest densification at lower sintering temperatures with 93% and 96% of the theoretical density at 1250 and 1300 ℃, respectively. Although YSZ-HT showed a higher sintering rate than TZ-8Y, a sintering temperature of 1350 ℃ was required for both the powders to reach 95% of the theoretical density. For the thin-film electrolytes, on the other hand, YSZ-HT showed the highest sintering rate with a dense microstructure at a co-sintering temperature of 1250 ℃. Our results indicate that besides the average particle size, other factors such as particle size distribution and post-processing play a significant role in determining the sintering rate and densification behavior of the YSZ powders. Additionally, a close match in the sintering shrinkage of the electrolyte and anode support is important for facilitating the densification of the thin-film electrolytes.

Aging performances for resisting low-temperature of three dental yttria-stabilized zirconia ceramic core materials

Background The low-temperature resistance aging performance of Yttria-stabilized tetragonal zirconia polycrystal （Y-TZP） is the key effective factor that influences the long-term success rate of prosthesis. The objective of this study was to test and compare the aging performances for resisting low temperature of Lava Frame, Cercon Smart, and Upcera Yttria-stabilized zirconia core materials, via analyzing the micro and the crystal phases of the materials, and measure the three-point bending strength and the fracture toughness. Methods The three zirconia green bodies were prepared as 60 test samples for three-point bending strength and as 60 test samples for fracture toughness. The test samples for three-point bending strength and fracture toughness were assigned to five groups and were treated respectively for 0, 5, 10, 15, and 20 hours to observe the micro and the crystal phases of the test samples. Then the three-point bending strength and fracture toughness were tested by X-ray diffraction （XRD）. Results The m phase content of Lava Frame was raised from 7.70% to 13.01%; the m phase content of Cercon Smart was raised from 4.95% to 8.53%; and Lava Frame is raised from 10.84% to 35.18%. The three-point bending strengths of the three zirconia core materials were higher than 1100 MPa and the fracture toughness was higher than 3 MPa.m^1/2. The three-point bending strength and the fracture toughness of Upcra zirconia decreased the most, followed by Lava Frame, and then by Cercon Smart. Conclusion The aging resistance sequences of the three zirconia core materials are, from strong to weak, Cercon Smart, Lava Frame, and Upcera.

Theoretical Aspects on Doped-Zirconia for Solid Oxide Fuel Cells:from Structure to Conductivity

Solid oxide fuel cells(SOFCs)are regarded to be a key clean energy system to convert chemical energy(e.g.H_(2) and O_(2))into electrical energy with high efficiency,low carbon footprint,and fuel flexibility.The electrolyte,typically doped zirconia,is the"state of the heart"of the fuel cell technologies,determining the performance and the operating temperature of the overall cells.Yttria stabilized zirconia(YSZ)have been widely used in SOFC due to its excellent oxide ion conductivity at high temperature.The composition and temperature dependence of the conductivity has been hotly studied in experiment and,more recently,by theoretical simulations.The characterization of the atomic structure for the mixed oxide system with different compositions is the key for elucidating the conductivity behavior,which,however,is of great challenge to both experiment and theory.This review presents recent theoretical progress on the structure and conductivity of YSZ electrolyte.We compare different theoretical methods and their results,outlining the merits and deficiencies of the methods.We highlight the recent results achieved by using stochastic surface walking global optimization with global neural network potential(SSW-NN)method,which appear to agree with available experimental data.The advent of machine-learning atomic simulation provides an affordable,efficient and accurate way to understand the complex material phenomena as encountered in solid electrolyte.The future research directions for design better electrolytes are also discussed.

Mechanical Behaviors of ZrO_2-Al_2O_3 Ceramic Composites with Y_2O_3 as Stabilizer

The ZrO2-Al2O3 ceramic composites were prepared by appropriate techniques with commercial ZrO2 and Al2O3 powders as raw materials and Y2O3 as stabilizer. The results indicate that with the introduction of Al2O3 into the ZrO2 matrix where the quantity of additive Y2O3 is 3.5% (mole fraction), the growth of ZrO2 grains is efficiently inhibited, which helps the ZrO2 grains exist in a metastable tetragonal manner; thus higher strength and toughness are acquired. When the content of alumina is 20% (mass fraction), the bending strength and fracture toughness of the composites are 676.7 MPa and 10 MPa·m1/2 respectively, the mechanical behaviors are close to those prepared with ZrO2 and Al2O3 powders synthesized through wet chemical approach. The mechanical behaviors of the composites are well improved owing to the dispersion toughening of alumina grains and phase transformation toughening of zirconia grains.

Electrical property of 8-mol% yttria-stabilized zirconia electrolyte by spark-plasma sintering

Spark-plasma sintering (SPS) process was used to sinter ZrO2 (8Y) powders, and a relative density of 99% has been reached at a low temperature (1350°C) and short dwelling time (10 min) compared to the conventional sintered identical samples (1450°C 4 h)(CS). By the X-ray diffraction (XRD) patterns, the microstructure of the SPS pellet and CS pellet are both indexed by the cubic unit cell (Fm3m). The finer crystallite size (D111) of the SPS pellet is 154 nm and D111 of the CS pellet is more than 1 μm. The AC impedance spectroscopy shows that the ionic conductivity of SPS pellet is different from that of CS pellet. The activation energy for the SPS ceramics, estimated from the slope in the range of 400–800°C, was 91 kJ mol?1, which is in good agreement with CS pellet (96 kJ mol?1), indicating that the conduction mechanism in SPS ceramics is similar to that in CS ceramics.

面向先进热障涂层的陶瓷材料研究进展

热障涂层利用陶瓷层的隔热性和抗腐蚀性可以有效保护航空发动机或陆用燃气轮机中热端部件的合金基体。然而,不断追求更高的服役温度会导致表面涂层的降解、分层和过早失效。为了满足未来先进热障涂层系统的服役需求,必须开发新的陶瓷材料。本文综述了近年来先进热障涂层陶瓷材料的研究进展,包括氧化钇部分稳定氧化锆(Yttria partially stabilized zirconia,YSZ)、A_(2)B_(2)O_(7)型化合物、稀土钽酸盐、稀土磷酸盐、高熵稀土陶瓷材料、磁铅石型六铝酸盐氧化物和自愈合材料,分别归纳了它们的性质和性能,总结各种材料现阶段发展的优势和不足,最后展望了热障涂层材料的发展方向,为开发新的热障涂层提供指导。

Investigation on the thermo-chemical reaction mechanism between yttria-stabilized zirconia （YSZ） and calciummagnesium-alumino-silicate （CMAS）

Thermal barrier coatings （TBCs） with Y2O3-stabilized ZrO2 （YSZ） top coat play a very important role in advanced turbine blades by considerably increasing the engine efficiency and improving the performance of highly loaded blades. However, at high temperatures, environment factors result in the failure of TBCs. The influence of calcium-magnesium-alumino-silicate （CMAS） is one of environment factors. Although thermo-physical effect is being paid attention to, the thermo-chemical reaction becomes the hot-spot in the research area of TBCs affected by CMAS. In this paper, traditional twolayered structured TBCs were prepared by electron beam physical vapor deposition （EB- PVD） as the object of study. TBCs coated with CMAS were heated at 1240℃ for 3 h. Additionally, 15 wt.% simulated molten CMAS powder and YSZ powder were mixed and heated at 1240℃ or 1350℃ for 48 h. SEM and EDS were adopted to detect morphology and elements distribution. According to XRD and TEM results, it was revealed that CMAS react with YSZ at high temperature and form ZrSiO4, Ca0.2Zr0.8O1.8 and Ca0.15Zr0.85O1.85 after reaction, as a result, leading to the failure of TBCs and decreasing the TBC lifetime.

不同钇含量氧化锆基热障涂层材料CMAS腐蚀行为研究

系统研究了不同YO1.5含量掺杂氧化锆基材料(8YSZ、20YSZ、38YSZ、55YSZ)以及纯氧化钇材料(Y_(2)O_(3))在1300℃下的CaO-MgO-Al_(2)O_(3)-SiO_(2)(CMAS)腐蚀行为。结果表明,不同钇含量氧化锆基材料表现出具有显著差异的CMAS腐蚀行为。对于YO1.5含量较低的8YSZ与20YSZ而言,腐蚀行为由溶解-再析出及晶界腐蚀所主导,前者析出小球颗粒ZrO_(2),后者的析出物则是直接沉积在原始ZrO_(2)表面形成核壳结构;随着YO1.5含量的增加,腐蚀行为逐渐转变成反应腐蚀,38YSZ以及55YSZ与CMAS熔盐快速反应结晶,形成一层连续致密、含磷灰石相的保护层,能够有效阻挡CMAS熔盐的进一步侵蚀,并且55YSZ所形成的保护层中磷灰石相的体积分数更多,抗CMAS腐蚀能力更佳;纯Y_(2)O_(3)样品也能与CMAS熔盐快速反应,从而形成一层致密的纯磷灰石层,抗CMAS腐蚀能力良好。因此,可以通过调控氧化锆基材料中的钇含量,从而调控热障涂层抗CMAS腐蚀能力。

氧化钇部分稳定氧化锆陶瓷涂层的高温耐久性辨析

氧化钇部分稳定的氧化锆(YSZ)作为热障涂层材料广泛应用于复杂高温工况,其优异的高温耐久性主要由不可相变介稳四方相(t′)所贡献。然而,目前对t′相可靠服役温度上限的界定较为模糊,主流观点仍停留在1200℃左右。基于此,采用大气等离子体喷涂(APS)工艺制备YSZ陶瓷涂层,经不同时效热处理,针对涂层微结构、相组成、烧结收缩和断裂韧性等变化进行分析研究。结果表明,经24 h@1400℃热处理附加7年室温存放后,陶瓷层未见单斜相;300 h@1400℃和300 h@1600℃热处理涂层中单斜相体积分数分别为3.55%和35.41%,且均未碎裂。300 h@1600℃涂层烧结线性收缩率为0.4%。高温时效热处理同时伴随晶粒生长和孔隙愈合,涂层抗折强度和断裂韧性随之增加,因而认为APS YSZ涂层可在1400℃下长时间(~300 h)服役。

氧化钇含量对YSZ热障涂层抗CMAS腐蚀性能的影响

系统研究大气等离子喷涂不同含量YO1.5掺杂氧化锆涂层(8YSZ、38YSZ和55YSZ)在1300℃下的环境沉积物(CMAS熔盐)腐蚀行为和机制。结果表明:8YSZ涂层会发生严重的CMAS熔盐腐蚀,在基体与CMAS界面处,通过溶解-再析出,生成非保护性、含Ca和较低Y含量的C-ZrO_(2),并有明显的晶界腐蚀现象;对于较高含量YO1.5掺杂的38YSZ和55YSZ涂层,随着反应的进行,除球状C-ZrO_(2)外,还生成保护性的磷灰石(apatite)和石榴石(garnet)产物,能够有效阻止CMAS熔盐的进一步侵蚀;并且,55YSZ涂层表现出优于38YSZ的抗CMAS熔盐腐蚀能力。从光学碱度而言,YO1.5含量越高,涂层与CMAS熔盐的反应活性越高,越容易生成在CMAS熔盐中稳定存在的产物;从反应进程来分析,高YO1.5含量的涂层材料能够促使Y3+在CMAS熔盐中的饱和,进而生成更为稳定、连续的物相(如磷灰石、石榴石),避免基体材料进一步与CMAS熔盐接触、反应,从而提高了抗CMAS腐蚀能力。

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。NiCrMoFe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。

ZnO掺杂8YSZ电解质材料的制备及其电池性能

使用机械混合,在8mol%Y_(2) O_(3) 稳定的ZrO_(2) (8YSZ)中添加ZnO量分别为0、1mol%、2mol%、3mol%、4mol%,分别在1300℃和1500℃下进行烧结制备高致密度高力学性能YSZ电解质材料(ZNOYSZ)电解质,对样品力学性质进行表征。由ZNOYSZ电解质作为支撑组装了单电池,对电池性能特征进行测试,结果显示:在相同工作条件下,ZNOYSZ单电池性能要优于YSZ单电池。3mol%ZnO添加YSZ时,电性能和力学性能效果最佳。750℃温度下,ZNOYSZ比YSZ单电池最大功率提升了70.85%、体积比功率值提升了18.25%、最大工作电流提升了25.62%、质量比功率值提升了51.96%。