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...

Crystal growth,structure and optical properties of Pr^(3+)-doped yttria-stabilized zirconia single crystals

The development of blue semiconductor light-emitting diodes(LEDs)has produced potential applications for Prdoped materials that can absorb blue light,especially crystals,and we now report structure and optical properties for high-quality Pr-doped single crystals of yttria-stabilized zirconia(YSZ)grown by the optical floating zone(FZ)method.X-ray diffraction(XRD)and Raman spectroscopy showed that all of the single crystal samples were in the cubic phase,whereas the corresponding ceramic samples contained a mixture of monoclinic and cubic phases.X-ray photoelectron spectroscopy(XPS)and electron paramagnetic resonance(EPR)spectroscopy showed that Pr was present as the Pr^(3+)ion in ceramic rods and single crystals after heating to high temperatures.The absorption and photoluminescence excitation(PLE)spectra of the Pr-doped YSZ crystals measured at room temperature showed strong absorption of blue light,while their photoluminescence(PL)spectra showed five emission peaks at 565 nm,588 nm,614 nm,638 nm,and 716 nm under450 nm excitation.The optimum luminescence properties were obtained with the crystal prepared using 0.15 mol%Pr_(6)O_(11),and those with higher concentrations showed evidence of quenching of the luminescence properties.In addition,the color purity of Pr-doped YSZ single crystal reached 98.9%in the orange–red region.

Preparation and Mechanical Properties of Zirconia Ceramics Doped with Different Y_(2)O_(3)Contents

The sintering behavior and mechanical properties of zirconia doped with 2.0mol%-3.0mol%Y_(2)O_(3)were studied by pressure-less sintering.The experimental results show that the densification temperature of zirconia ceramics increases gradually with the decrease of Y_(2)O_(3)doping content by which decreases the sintering driving force due to the lower oxygen vacancy concentration of the systems.Furthermore,the bending strength and fracture toughness of the prepared zirconia ceramics increase with the decrease of Y_(2)O_(3)doping content.It can be attributed to the fact that the phase stability of tetragonal zirconia decreases with the decrease of Y_(2)O_(3)doping content,which is easier to induce"phase transformation toughening"and dissipate impact energy.The relative density,bending strength and fracture toughness of 2.0 mol%Y_(2)O_(3)doped zirconia ceramics(2.0Y-ZrO_(2))sintered at 1525℃are 99.00%,1256.65±20.82 MPa and 9.85±0.13 MPa·m^(1/2),respectively.

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.

Influence of characteristics of stabilized zirconia electrolyte on performance of cermet supported tubular SOFCs

Ni-Al2O3 cermet supported tubular SOFC was fabricated by thermal spraying. Flame-sprayed Al2O3-Ni cermet coating plays dual roles of a support tube and an anode current collector. 4.5mol.% yttria-stabilized zirconia (YSZ) and 10mol.% scandia-stabilized zirconia (ScSZ) coatings were deposited by atmospheric plasma spraying (APS) as the electrolyte in present study. The electrical conductivity of electrolyte was measured using DC method. The post treatment was employed using nitrate solution infiltration to densify APS electrolyte layer for improvement of gas permeability. The electrical conductivity of electrolyte and the performance of single cell were investigated to optimize SOFC performance. The electrical conductivity of the as-sprayed YSZ and ScSZ coating is about 0.03 and 0.07 S·cm-1 at 1000 ℃, respectively. The ohmic polarization significantly influences the performance of SOFC. The maximum output power density at 1000 ℃ increases from 0.47 to 0.76 W·cm-2 as the YSZ electrolyte thickness reduces from 100 μm to 40 μm. Using APS ScSZ coating of about 40 μm as the electrolyte, the test cell presents a maximum power output density of over 0.89 W·cm-2 at 1000 ℃.

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.

高密度无色合成立方氧化锆的宝石学特征及密度成因

近年来,广西梧州出现一种高密度无色合成立方氧化锆(CZ),但目前对于此种人工宝石的宝石学特征研究很少。利用傅里叶红外光谱仪、X射线粉末衍射仪、X射线荧光光谱仪及LA-ICP-MS对这种高密度CZ样品的宝石学特征进行了系统研究。研究表明,高密度CZ的相对密度约为6.60,在长短波紫外光下呈强蓝色荧光;普通密度CZ样品的相对密度约为5.96,荧光惰性,其余常规宝石学参数二者几乎一致。高密度CZ中含有约32 wt%的Gd元素,确定其为Gd_(2)O_(3)作稳定剂,推测Gd元素的相对原子质量偏高而导致高密度CZ样品的密度偏高。根据LA-ICP-MS数据计算出分子式,推算高密度CZ样品的相对密度应为6.93,与实测不符。由此推断,影响其密度的因素不仅是Gd元素的相对原子质量。由于离子半径Gd^(3+)相较于Y^(3+)和Zr^(4+)偏大,推测Gd^(3+)半径偏大导致晶体常数发生变化,致使密度少许下降。

Thermal Transport in Nanoporous Yttria-Stabilized Zirconia by Molecular Dynamics Simulation

Yttria-stabilized zirconia(YSZ) is widely used as thermal barrier coatings(TBCs) to reduce heat transfer between hot gases and metallic components in gas-turbine engines. Porous structure can generally reduce the lattice thermal conductivity of bulk material, so porous YSZ can be potentially used as TBCs with better thermal performance. In this work, we investigate the thermal conductivity of nanoporous YSZ using the nonequilibrium molecular dynamics(NEMD) simulation, and comprehensively discuss the effects of cross-sectional area, pore size, structure length, porosity, Y_2O_3 concentration and temperature on the thermal conductivity. To compare with the results of the NEMD simulation, we solve the heat diffusion equation and the gray Boltzmann transport equation(BTE) to calculate the thermal conductivity of the same porous structure. From the results,we find that the thermal conductivity of YSZ has a weak dependence on the structure length at the length range from 10 to 26 nm, which indicates that the majority of heat carriers have very short mean free path(MFP) but there exists small percentage(about 3%) of phonons with longer MFP(larger than 10 nm) contributing to the thermal conductivity. The thermal conductivity predicted by NEMD simulation is smaller than that of solving heat diffusion equation(diffusive limit) with the same porous structure. It shows that the presence of pores affects phonon scattering and further affects the thermal conductivity of nanoporous YSZ. The results agree well with the solution of gray BTE with a average MFP of 0.6 nm. The thermal conductivity of nanoporous YSZ weakly depends on the Y_2O_3 concentration and temperature, which shows the phonons with very short MFP play the major contribution to the thermal conductivity. The results help to better understand the heat transfer in porous YSZ structure and develop better TBCs.

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.

Hot corrosion mechanism of yttria-stabilized zirconia powder in the presence of molten Na_(2)SO_(4)+V_(2)O_(5) salts

The hot corrosion behavior of yttria-stabilized zirconia(YSZ)powder specimens exposed to Na_(2)SO_(4)/V_(2)O_(5) salts mixtures at high temperature was evaluated.Initial tests were carried out at 1000℃ for 10 h,the salt concentrations varied from 0.1 wt%to 1.00 wt%,and the Na_(2)SO_(4)/V_(2)O_(5) mass ratios were between 0.20 and 0.44 following a factorial design 22.X-ray diffraction(XRD)analyses of the tested samples showed with a confidence of95%that the mixture composed of 32 wt%Na_(2)SO_(4)+68 wt%V_(2)O_(5),and 1.00 wt% salt concentration led to high destabilization of the t’-YSZ phase and formation of YVO_(4) products.A second set of experiments were conducted to assess the influence of temperature on the hot corrosion response of the YSZ in the range between 490 and 1100℃.Thermogravimetric analysis(TGA)experiments and Rietveld adjustments of XRD patterns showed that the mass loss of the samples varied with testing temperature and also that the major destabilization of tetragonal phase occurred at 900℃.

Fabrication,microstructure,and properties of 8 mol%yttria-stabilized zirconia(8YSZ)transparent ceramics

Fine grained 8 mol%yttria-stabilized zirconia(8YSZ)transparent ceramics with high optical and mechanical properties were fabricated by air pre-sintering and hot isostatic pressing(HIP)using commercial 8YSZ powders as the raw material.The pre-sintered ceramics with fine grains and appropriate relative density play a key role to achieve high transparency and suppressed grain size after HIP post-treatment at relatively low temperatures.With the increase of HIP temperature from 1350 to 1550℃,the in-line transmittance of 8YSZ ceramics at 600 nm increases from 56.9%to 71.5%(2.5 mm in thickness),and the average grain size increases from 2.4 to 16.3μm.The corresponding bending strength of 8YSZ transparent ceramics decreases from 328±20 to 289±19 MPa,the hardness(H)decreases from 12.9±0.1 to 12.5±0.2 GPa,and the fracture toughness(KIC)decreases from 1.30±0.02 to 1.26±0.03 MPa·m^(1/2).Systematical investigations were carried out to study the combination of high optical transparency and excellent mechanical properties in 8YSZ ceramics.

Self-supported yttria-stabilized zirconia mesocrystals with tunable mesopores prepared by a chemi-thermal process

Mesoporous mesocrystals are highly desired in catalysis,energy storage,medical and many other applications,but most of synthesis strategies involve the usage of costly chemicals and complicated synthesis routes,which impede the commercialization of such materials.During the sintering of dense ceramics,coarsening is an undesirable phenomenon which causes the growth of the grains as well as the pores hence hinders the densification,however,coarsening is desired in the sintering of porous ceramics to expand the pore sizes while retaining the total pore volume.Here we report a chemi-thermal process,during which nanocrystallite aggregates were synthesized by hydrothermal process and then converted to the product by sintering.Through this strategy,we synthesized mesoporous self-supported mesocrystals of yttria-stabilized zirconia with tunable pore size and the process was then scaled-up to industrial production.The thermal conductivity measurement shows that the mesoporous powder is a good thermal isolator.The monolith pellets can be obtained by SPS sintering under high pressure and the mesoporosity is retained in the monolith pellets.This work features facile and scalable process as well as low cost raw chemicals making it highly desirable in industrial applications.

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℃) and short dwelling time (10 min) compared to the conventional sintered identical samples (1450℃ 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 mm. 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℃, 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.

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.

聚合络合法制备钙稳定氧化锆

钙稳定氧化锆 (CSZ)是根据有机物聚合络合法 ,即按照Pechini_type型反应制取的 .将一定量的柠檬酸、乙二醇混合液同ZrOCl2 ·8H2 O和Ca(Ac) 2 ·H2 O在 15 0℃左右发生聚合反应形成一透明的树脂状物质 ,尔后在 45 0℃左右进行炭化 ,得到黑色的混合氧化物前驱体 .对前驱体进行差热和热重分析 ,确定灼烧温度在 10 0 0℃时 ,可得到白色的粉末 .经XRD分析表明 ,得到了立方型的稳定氧化锆 ,晶胞参数为a =5 .10

微波水热合成ZrO_2-8%Y_2O_3纳米粉体

以Zr(OH)4和Y(OH)3的共沉淀为前驱体,在碱性介质中用微波水热法合成摩尔分数为8%的氧化钇稳定氧化锆(yttria stabilized cubic zirconia,YSZ)纳米粉体.通过X射线粉末衍射仪、透射电镜和等离子发射光谱等表征粉体的性能.研究了微波水热法的反应温度、时间和前驱物浓度对反应产物形貌、粒度等的影响.获得了制备具有纳米立方相结构的YSZ粉体的最佳工艺参数:粉体粒度为5～10 nm,产物纯度为99%.结果表明:温度为200℃时,产物粒径较小且均匀.微波水热制备YSZ的最佳反应时间为20～40 min.前驱物中Zr4+的最佳浓度为0.2 mol/l.增大碱性介质KOH的浓度对产物的晶型和粒度影响不大.

ZrO2晶相对锰铈系SCR催化剂脱硝活性的影响

采用浸渍法制备了以nm级c-Zr O2(立方相Zr O2)、t-Zr O2(四方相Zr O2)和m-Zr O2(单斜相Zr O2)为载体的负载型Mn Ox-Ce O2/Zr O2催化剂,并在连续流动固定床反应器上考察了催化剂的NH3-SCR低温脱硝性能.结果表明,催化剂脱硝性能良好,当Mn Ox负载量(以w计)为15.0%时,以c-Zr O2为载体的催化剂脱硝效率在103℃即可达到100%.在相同活性组分负载量和反应温度条件下,各催化剂的低温脱硝活性体现出Mn Ox-Ce O2/c-Zr O2>Mn Ox-Ce O2/t-Zr O2>Mn Ox-Ce O2/m-Zr O2的规律,因此对Mn Ox负载量为5.0%的Mn Ox-Ce O2/Zr O2系列催化剂进行进一步表征,以探究该规律的内在影响因素.BET测试结果表明,以c-Zr O2为载体的催化剂的比表面积最大,达到39.67 m2/g,更有利于气体和催化剂表面活性位的接触.XPS测试结果表明,以c-Zr O2为载体的催化剂表面晶格氧含量最丰富,有助于Lewis酸性位的形成.TPR和TPD测试图谱中的峰强及峰面积表明,以c-Zr O2和t-Zr O2为载体的催化剂表面主要存在Lewis酸性位;而在以m-Zr O2为载体的催化剂表面,Lewis酸性位较多,同时还存在少量的Brnsted酸性位.研究显示,Zr O2晶型结构变化引起Mn Ox-Ce O2/Zr O2催化剂的比表面积、表面活性酸性位的不同是产生晶型效应的原因所在;采用Zr O2作为负载型低温SCR催化剂载体时,以立方相晶型结构为最佳.

冷冻干燥法制备MgO－ZrO_2超细粉末

采用冷冻干燥法制得了烧结性能良好的ｃ－ＺｒＯ_２（１０％ＭｇＯ，以摩尔计）超细粉末，并对冷冻干燥工艺进行了探索。粉末的煅烧温度为８００℃，成型后试样经１６００℃，２ｈ烧成，相对体积密度达到了９５％以上，且全部为立方相。