稳定化氧化锆的晶界导电模型

晶界空间电荷层在高纯的稳定化ZrO₂的晶界电阻中起着重要作用，以此为基础，提出了一个稳定化ZrO₂的晶界导电模型，根据这个模型分析了Ca,Y和Al的晶界偏聚对稳定化ZrO₂的晶界导电性的影响，并同时分析了被广泛应用的以Bauerle等效电路为基础的晶界电阻测量方法的局限性，以及一些晶界性能表征参量的物理意义及欠妥之处. 关键词：     

不同应力场中马氏体形核的择优取向

系统地模拟计算了不同方位四方相ZrO₂(T)椭球片分别在拉、压、剪应力诱导下发生ZrO₂(T)→ZrO₂(M)马氏体相变时系统应变能的变化.并用能量极小准则确定了有利的形核方位.结果表明相变中伴随较大的剪切变形将使马氏体形核呈现明显的择优取向;不同应力场诱导相变的临界应力相差很大. 关键词：     

纳米晶ZrO2：Dy3+的光致发光和能量传递性质

研究了Dy³⁺离子掺杂的ZrO₂纳米粉体的光致发光性质。观测到Dy³⁺离子的室温强特征发射和浓度猝灭现象以及基质ZrO₂与Dy³⁺离子之间的能量传递过程。发现了煅烧温度对样品的晶相有明显的影响,随着煅烧温度的变化,晶相也随之改变。晶相的改变使样品的荧光发射产生较大的差异,并观测到两个发射中心。通过对荧光强度与激活离子Dy³⁺离子浓度的关系研究发现,Dy³⁺离子在纳米ZrO₂基质中存在浓度猝灭现象,最佳掺杂浓度取决于ZrO₂基质的晶相,不同晶相导致不同的猝灭浓度,当基质晶相表现为四方相时,猝灭浓度为0.5%,而基质晶相为混合相时,猝灭浓度为1%。能量传递也依赖于样品的晶相。当煅烧温度为950℃时能量传递效果最好,并且从微观结构上给出了解释基质与Dy³⁺离子之间的能量传递的模型。     

Al2O3-Y2O3-ZrO2三相复合陶瓷的介电谱研究

采用传统的固相反应法,在1400–1500 ℃下烧结,制备得到Al₂O₃-Y₂O₃-ZrO₂三相复合陶瓷.样品的结构、形貌和电性能分别用X射线衍射(XRD)、扫描电子显微镜(SEM)及介电谱表征.XRD表明此三相复合体系无其他杂相,加入Y₂O₃及ZrO₂后使得Al₂O₃成瓷温度降低;SEM表明此体系晶粒直径为200–500 nm,并且样品随烧结温度的升高而变得更加致密,晶界更加清晰;介电损耗谱中出现峰值弛豫现象,根据Cole-Cole复阻抗谱得出其为非德拜弛豫. 关键词： 2O₃-Y₂O₃-ZrO₂三相陶瓷')" href="#">Al₂O₃-Y₂O₃-ZrO₂三相陶瓷 介电弛豫 阻抗谱 热导率     

980 nm激发下Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的上转换发光特性

通过固相反应法制备了Er³⁺/Yb³⁺共掺杂ZrO₂-Al₂O₃粉末的样品，并对样品在980nm激光激发下的上转换发光特性进行了研究.从发射光谱可以发现，在可见光范围内有3个强的发光带，一个位于654nm附近的红光带和两个分别位于545nm、525nm附近的绿光带，分别对应于Er³⁺离子的以下辐射跃迁：⁴F_9/2→⁴I_15/2、⁴S_3/2→⁴I_15/2、 ²H_11/2→⁴I_15/2.其中又以Er³⁺离子的⁴F_9/2→⁴I_15/2跃迁产生的红色荧光辐射最强.对其上转换发光机制进行了分析，发现这三个发光过程都是双光子过程.对样品粉末进行了XRD检测，发现ZrO₂主要以立方相为主，并且计算得到了这种立方结构的晶格常数.Al₂O₃固溶于ZrO₂中，Al³⁺嵌入ZrO₂后产生氧空位，导致ZrO₂晶体的对称性降低，这种结构变化更有利于提高上转换效率，即上转换发光强度增强. 关键词： 3+/Yb³⁺')" href="#">Er³⁺/Yb³⁺ 上转换 2-Al₂O₃')" href="#">ZrO₂-Al₂O₃ 荧光 稀土     

Bi，Sb合金化对AZ91镁合金组织、性能影响机理研究

利用大角重位点阵模型建立了AZ91镁合金α相［0001］对称倾斜晶界原子结构模型，应用实空间的连分数方法计算了Mg合金的总结构能，合金元素引起的环境敏感镶嵌能及原子间相互作用能，讨论了主要合金元素Al及Bi，Sb在AZ91中的合金化行为.计算结果表明，Al，Bi，Sb固溶于α相内或晶界区使总结构能都降低，起到固溶强化作用；合金元素在AZ91α相内趋于均匀分布，在晶界区易占位于三角椎上部.AZ91镁合金中加入Bi或Sb时，Bi或Sb比Al容易偏聚于晶界，从而抑制了Al在晶界的偏聚，促进基体中连续的Mg₁₇Al₁₂相的析出，提高AZ91合金室温性能； AZ91合金中(α相内和晶界区)主要合金元素Al和微加元素Bi，Sb都能够形成有序相Mg₁₇Al₁₂，Mg₃Bi₂或Mg₃Sb₂，且在晶界区形成的量大.Bi，Sb加入AZ91合金中，由于Bi，Sb抑制Al在晶界的偏聚，晶界区主要析出相为Mg₃Bi₂或Mg₃Sb₂，提高镁合金高温性能. 关键词： 电子理论 合金化 晶界偏聚 镁合组织与性能     

Al86-xFe14+x准晶相合金的M?ssbauer谱

本文研究了Al_86-xFe_14+x(x=0,2,4,6,8.5)准晶相合金的M?ssbauer谱,结果表明对x=0的Al₈₆Fe₁₄合金中以decagonal准晶相为主,谱拟合结果为两套面积积分比为1.69,近于黄金分割的亚谱组成,支持了准晶相为两种“Penrose”多面体组成的观点。当x增加时,出现的晶态含量增加;x=8.5时,几乎全部为晶态Al₃Fe相。 关键词：     

ZnO-Bi2O3-Sb2O3-BaO系陶瓷的晶界相与抗退降性能

在通常的ＺｎＯ－Ｂｉ₂Ｏ₃－Ｓｂ₂Ｏ₃系电压敏陶瓷中，加入能构成压敏特性的钡添加剂，发现除已知的Ｂｉ₂Ｏ₃和Ｚｎ_2．３３Ｓｂ_０．６７Ｏ₄晶界相以外，还出现新的晶界相，分析表明是固溶有微量其它成分的偏锑酸钡（ＢａＳｂ₂Ｏ₆）晶相。同时还发现，ＢａＳｂ_{2关键词：}     

SND6800球磨剂对纳米ZrO2水悬浮液性质的影响

研究了SND6800球磨剂对纳米ZrO₂水悬浮液性质的影响。结果表明。粒径小于15nm ZrO₂在SND6800球磨剂的水相中球磨2h制备的悬浮液,可稳定存在14天。SND6800球磨剂与ZrO₂的质量比为3.5:100,悬浮液的吸光度较小、表面张力较大、黏度较小、沉降率接近最低值。SND6800球磨剂的含量对悬浮液的密度和pH值影响不大。     

基于透射光谱确定溶胶凝胶ZrO2薄膜的光学常数

基于溶胶凝胶ZrO₂薄膜的紫外/可见/近红外透射实验光谱,采用Swanepoel方法结合Wemple-DiDomenico色散模型,方便地导出了ZrO₂薄膜在200—1200nm波长范围内的光学常数,包括折射率、色散常数、膜层厚度、吸收系数及能量带隙.研究发现,溶胶凝胶ZrO₂薄膜具有高折射率(1.63—1.93,测试波长为632.8nm)、低吸收和直接能量带隙(4.97—5.63eV) 等光学特性,而且其光学常数对薄膜制备过程中的重要工艺 关键词： 光学常数 Swanepoel方法 2薄膜')" href="#">ZrO₂薄膜 热处理     

Different conduction behaviors of grain boundaries in SiO2-containing 8YSZ and CGO20 electrolytes

Both doped zirconia and ceria have been widely recognized as promising electrolytes in solid oxide fuel cells (SOFC). Total conductivity is an important parameter to evaluate solid electrolytes. It is well know that the contribution to the total conductivity by grain boundaries is especially pronounced for SiO₂-contaminated electrolytes. In this study, we report on the different conduction behaviors of grain boundaries (GB) found in SiO₂-containing (impure) 8YSZ (8 mol% Y₂O₃-doped ZrO₂) and CGO20 (10 mol% Gd₂O₃-doped CeO₂) ceramics. In the grain size range (∼ 0.5–10 μm) studied, the GB conductivity of impure CGO20 ceramics constantly decreases with increasing grain size, in contrast to that observed in impure 8YSZ electrolytes whose GB conductivity increases almost linearly with grain size. It is also found that the variation in GB conductivity versus grain size is different from case to case, depending on the sintering/annealing conditions used to fabricate the ceramics. Two mechanisms were proposed to explain the GB behaviors of the impure 8YSZ and CGO20 ceramics. For doped ceria, the GB phases are supposed to be inert, which do not react with or dissolve into the matrix. Increasing sintering temperature leads to not only grain growth but also change in viscosity and wetting nature of the GB phases. These two factors promote further propagation of the GB phases along the grain boundaries, leading to an increased GB coverage fraction. For doped zirconia, however, the major factor dominating the GB conduction is the further dissolution of SiO₂ into zirconia lattice as a result of increase in sintering temperature or/and time. In addition, we will also evaluate and discuss the validities of the three models that are widely used to analyze the GB conduction in solid electrolytes.     

Optimised NASICON ceramics for Na+ sensing

NASICON dense ceramics were obtained from solid state reaction between SiO₂, Na₃PO₄·12H₂O and two different types of zirconia: monoclinic ZrO₂ and the yttria-doped tetragonal phase (ZrO₂)_0.97(Y₂O₃)_0.03. Higher temperatures were needed to obtain dense samples of the yttrium free composition (1265 °C). The electrical conductivity, at room temperature, of the yttria-doped samples sintered at 1230 °C (0.20 S/m) is significantly higher than the value obtained with the material prepared from pure ZrO₂. The impedance spectra show that the differences in conductivity are predominantly due to the higher grain boundary resistance of the undoped ceramics, probably due to formation of monoclinic zirconia and glassy phases along the grain boundary. Further improvement of the electrical conductivity could be achieved after optimization of the grain size and density of grain boundaries. A maximum conductivity value of about 0.27 S/m at room temperature was obtained with the yttria-doped samples sintered at 1220 °C for 40 h. Yttria-doped and undoped ceramics were tested as Na⁺ potentiometric sensors. The detection limit of the yttria-doped sample (10⁻⁴ mol/l) was one order of magnitude lower than the obtained with the undoped material. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16 – 22, 2001.     

High-Temperature Behavior of SiO2 at Grain Boundaries in TZP

The chemical reaction between SiO₂ and tetragonal zirconia polycrystal (TZP) was directly observed using a TEM in-situ heating technique in order to understand the behavior of SiO₂ in TZP at high temperatures. Their dynamic interaction was recorded up to about 1400°C using a CCD camera-video system connected to the TEM. Most of SiO₂ phase dissolved into the ZrO₂ grains above 1300°C. On the other hand, during cooling from the high temperature to around 400°C, amorphous SiO₂ reprecipitated from the surface of ZrO₂ grains and formed a thin layer around the ZrO₂ grains. This result agrees well with the fact that silicon segregates in the vicinity of grain boundaries in SiO₂-doped TZP. In order to confirm the grain boundary segregation at high temperatures, we investigated grain boundaries in quenched specimens by high resolution electron microscopy (HREM), energy dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS). It was found that no amorphous phase was present between two adjacent grains in the quenched samples. EDS analysis revealed that silicon segregated at the grain boundaries and that the segregation layer was wider than that in as-sintered specimens. The electron energy loss near edge structure (ELNES) of O K-edge was measured from both grain boundary and grain interior in quenched specimen, and their spectra were interpreted by a first principles molecular-orbital (MO) calculation using the discrete-variational (DV)-X method.     

Solid–state diffusion–controlled growth of the phases in the Au–Sn system

The solid state diffusion-controlled growth of the phases is studied for the Au–Sn system in the range of room temperature to 200 °C using bulk and electroplated diffusion couples. The number of product phases in the interdiffusion zone decreases with the decrease in annealing temperature. These phases grow with significantly high rates even at the room temperature. The growth rate of the AuSn₄ phase is observed to be higher in the case of electroplated diffusion couple because of the relatively small grains and hence high contribution of the grain boundary diffusion when compared to the bulk diffusion couple. The diffraction pattern analysis indicates the same equilibrium crystal structure of the phases in these two types of diffusion couples. The analysis in the AuSn₄ phase relating the estimated tracer diffusion coefficients with grain size, crystal structure, the homologous temperature of experiments and the concept of the sublattice diffusion mechanism in the intermetallic compounds indicate that Au diffuses mainly via the grain boundaries, whereas Sn diffuses via both the grain boundaries and the lattice.     

Study on preparation and properties of molybdenum alloys reinforced by nano-sized ZrO<Subscript>2</Subscript> particles

The nano-sized ZrO₂-reinforced Mo alloy was prepared by a hydrothermal method and a subsequent powder metallurgy process. During the hydrothermal process, the nano-sized ZrO₂ particles were added into the Mo powder via the hydrothermal synthesis. The grain size of Mo powder decreases obviously with the addition of ZrO₂ particles, and the fine-grain sintered structure is obtained correspondingly due to hereditation. In addition to a few of nano-sized ZrO₂ particles in grain boundaries or sub-boundaries, most are dispersed in grains. The tensile strength and yield strength have been increased by 32.33 and 53.76 %.     

Ion conductivity,structural features,and multifractal properties of grain boundaries in CuCr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>V<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>2</Subscript>

The ion conductivity, crystal structure, and multifractal parameters of the sections of grain boundaries in CuCr_1?x V _x S₂ superionic conductors with 0 ≤ x ≤ 0.3 have been investigated. It is established that an increase in the surface area of grain boundaries and complication of their shape in such compounds facilitate ion transport. The effect of crystal structure peculiarities on the grain structure of these compounds has been revealed.     

AES/STEM grain boundary analysis of stabilized zirconia ceramics

Semiquantitative Auger Electron Spectroscopy (AES) on pure monophasic (ZrO₂)_0.83(YO_1.5)_0.17 was used to determine the chemical composition of the grain boundaries. Grain boundary enrichment with Y was observed with an enrichment factor of about 1.5. The difference in activation energy of the ionic conductivity of the grain boundary compared with the bulk can be explained by the Y segregation.When Bi₂O₃ is introduced into this material and second phase appears along the grain boundaries of the cubic main phase. Energy dispersive X-ray analysis (EDS) on a scanning transmission electron microscope (STEM) shows an enrichment of bismuth at the grain boundaries of this second phase.     

Comparison of Segregation Behaviors for Special and General Boundaries in Polycrystalline Al2O3 with SiO2-TiO2 Impurities

A systematic study of grain boundaries with an elongated grain morphology in TiO₂-doped polycrystalline Al₂O₃ materials with SiO₂ impurities is reported in this paper. Over 20 grain boundaries, all having common (0001) basal plane surface on one side, were investigated by using HRTEM and analytical TEM. A few of them were basal plane twin boundaries or other non-wetting boundaries, and the majority of grain boundaries were covered by amorphous phases, either as continuous films or with small pockets bounded by surface facets. Si and Ti were segregated to all boundaries, however, two categories of segregation were observed. Excesses of both segregants were between 1.0–4.0 atom/nm² at special and non-wetting boundaries, while they were in the range of 7.0–30 atom/nm² at boundaries with amorphous phases. A variation of amorphous film thickness was also observed, which has a clear relation with Si excess level while Ti excess remained at the same level. This observation suggests that the amorphous phases were primarily made of SiO₂ but Ti segregants were attached to grain surfaces. The variation in thickness of SiO₂-based film is strongly related to the surface structure of anisotropic Al₂O₃ grains.     

Phase transformation of ZrO2 nanoparticles produced from zircon

This article focuses on the phase transformation of zirconia (ZrO₂) nanoparticles produced from zircon using a bottom-up approach. The influence of mechanical milling and thermal annealing on crystalline phase transformation of ZrO₂ nanoparticles was explored. It was found that the iron oxide, as an inherent impurity present in ZrO₂ nanoparticles, produced from zircon stabilises the cubic phase after calcination at 600°C. The stabilised cubic phase of ZrO₂ nanoparticles was disappeared and transformed into partial tetragonal and monoclinic phases after mechanical milling. The phase transformation occurred on account of the crystal defect induced by high-energy mechanical milling. The destabilisation of cubic phase into monoclinic phase was observed after the thermal annealing of ZrO₂ nanoparticles at 1000°C. The phase transitions observed are correlated to the exclusion of iron oxide from the zirconia crystal structure.