Nanodomain formation and distribution in Gd-doped ceria

A comprehensive study, with a combination of diverse analytical techniques, was performed to investigate nanodomain formation and distribution in gadolinium-doped ceria. It is illustrated that the nanodomain formation, originating from the aggregation and segregation of dopant cations together with associated charge-compensating oxygen vacancies, is ubiquitous throughout doped ceria. The formation of nanodomains is not limited to bulk areas as previously reported but exists at grain boundaries as well. With enhanced ordering level, such nanodomains formed at grain boundaries will decrease the ionic conductivity as a result of hindered the mobility of oxygen vacancies in doped ceria. Particularly, the nanodomains formed at grain boundaries, with strong defect interactions due to enrichment of dopants and ordered oxygen vacancies, are suggested to be another possible reason for the grain-boundary resistance, other than the widely accepted space-charge layers.     

Conductivity of the nanostructured ceramic material Zr<Subscript>0.88</Subscript>Sc<Subscript>0.1</Subscript>Ce<Subscript>0.01</Subscript>Y<Subscript>0.01</Subscript>O<Subscript>1.955</Subscript> prepared from mechanically activated powders

The structure of the Zr_0.88 Sc_0.1Ce_0.01Y_0.01O_1.955 solid solution, a candidate for the use as a solid electrolyte in fuel cells with a low temperature, has been investigated using x-ray powder diffraction and Raman spectroscopy. Single-phase ceramic materials have been produced from powders prepared by the mechanochemical synthesis from ZrO₂ nanoprecursors purified of the impurities introduced during grinding of commercial zirconia. The solid solution has a rhombohedral structure at room temperature owing to the partial ordering of oxygen vacancies. The electrical conductivity of the ceramic materials sintered at temperatures below 1570 K exhibits a hysteresis due to the delay of the martensitic transition from the cubic phase to the rhombohedral phase upon cooling of the sample. The nanostructured ceramic materials are characterized by a high mechanical strength and unusually close values of the activation energies for bulk and grain-boundary electrical conduction.     

Effect of grain-boundary diffusion acceleration during recrystallization in submicrocrystalline metals and alloys prepared by severe plastic deformation

The results of studying the effect of grain-boundary diffusion acceleration during the annealing of submicrocrystalline (SMC) materials prepared by severe plastic deformation techniques are described. It is shown that the grain-boundary diffusion coefficient during recrystallization of SMC materials depends on the density of lattice dislocations and the pattern and rate of migration of the grain boundaries. It is found that, in SMC metals that undergo anomalous grain growth during annealing, the grain-boundary diffusion coefficient increases and its activation energy decreases. In SMC materials in which the recrystallization process exhibits conventional behavior, the diffusion properties of grain boundaries hardly differ from the equilibrium properties. Expressions describing the dependence of the grain-boundary diffusion coefficient on the migration rate of grain boundaries, as well as the thermodynamic and crystallographic parameters of the material, are derived. The calculation results are compared with the experimental data.     

Grain growth in sol–gel derived alumina–zirconia composites

Grain-growth kinetics in sol–gel derived alumina–zirconia composites, containing 20 wt% ZrO2 stabilized with 0, 3 and 6 mol% ceria have been examined. The growth of alumina grains was effectively retarded by zirconia particles and a lake of abnormal growth was evident. Coupled grain growth was observed, but only if the required minimal sintering conditions (i.e. minimal sintering density) were reached. Measured grain-growth exponents indicate that the grain-boundary diffusion-controlled growth is probably the dominant rate-controlling mechanism in this system. © 1998 Chapman & Hall     

The relationship between crystal misorientation and conductive mode contrast of grain boundaries in additive-free zinc oxide

Grain boundaries in additive-free ZnO show different types of conductive mode contrast, depending on the electrical properties. Electron beam scattering patterns have been used to determine the misorientation of grain boundaries showing certain types of conductive mode contrast in order to correlate electrical properties with grain-boundary structure. No correlations were apparent using the coincident-site lattice model, but other criteria suggest that grain-boundary electrical properties may be crystallographically controlled. More detailed analysis will require the full determination of the grain-boundary plane. This revised version was published online in November 2006 with corrections to the Cover Date.     

Studies of structural,optical, and electrical properties associated with defects in sodium-doped copper oxide (CuO/Na) nanostructures

In the present paper, we report a detailed study on the sodium (Na) doping-induced modifications in the copper oxide (CuO) nanostructure and its properties. A facile and sustainable sol–gel synthesis approach was employed for the preparation of high-quality pristine CuO- and Na-doped CuO nanostructures(1.0, 3.0, 5.0 and 7.0 mol% doping levels, CuO/Na) with controlled shape and composition. Due to the remarkable difference in the ionic radii of Cu²⁺ (0.73 Å) and Na⁺ (1.02 Å), Na⁺ substitution in place of Cu²⁺ generates strain/distortions in CuO lattice. The XRD analysis reveal the structural alteration from monoclinic to cubic symmetry with increase in doping level and also reveal the phase purity up to 3% doping level, and beyond this (i.e., for 5 and 7% doping level) small amount of impurity phase corresponding to Na₂O was observed. The FTIR results further confirmed the presence of the Na–Cu–O stretching vibrations at higher Na-doped samples. Morphology of the samples indicates that the Na-doped CuO nanostructures exhibit less agglomeration compared to pristine CuO nanoparticles. The presence of Na in CuO lattice were found to greatly enhances optical and electrical properties owing to the formation of defects like copper vacancies and oxygen vacancies at the grain boundaries of the nanoparticles with increased doping of Na.     

Effect of laser power on electrical conductivity of BaTi5O11 films prepared by laser chemical vapor deposition method

BaTi₅O₁₁ films were prepared on Pt/Ti/SiO₂/Si substrates by a laser chemical vapor deposition method. The effect of laser power (P _L) on the electrical conductivity of the BaTi₅O₁₁ films was investigated. The electrical resistivity of the grains was much higher than that of the grain boundaries, which indicated that the electrical conductivity along the grain boundary was dominant. For the BaTi₅O₁₁ films, the conduction was mainly attributed to oxygen vacancies, and the electrical conductivity was strongly affected by their microstructures and the concentration of the charge carriers. With increasing the P _L, the grain size increased and the grain-boundary density decreased, which resulted in the decrease of the electrical conductivity. At the same time, the increase of T _dep led to higher concentration of charge carriers, which resulted in the increase of electrical conductivity.     

Size dependent grain-boundary conductivity in doped zirconia

The oxygen vacancy distributions at a grain boundary and resulting grain-boundary conductivities were calculated as a function of grain size, with an emphasis on nanocrystalline materials. The cause for the “intrinsic” grain-boundary blocking effect is analyzed, and the variation of the grain-boundary conductivity with grain size is discussed. Compared with literature experimental results, the calculation results are reasonable. Finally, the feasibility of Bauerle's equivalent electrical circuit for nanocrystalline materials is evaluated.     

An investigation into microwave bonding mechanisms via a study of silicon carbide and zirconia

It is known that the glassy grain-boundary phase present in low-purity aluminas has two primary functions during direct microwave bonding. Firstly, it increases the dielectric loss of the host ceramic, allowing heating to occur; secondly, the bonding mechanism itself has been found to be based on viscous flow of the glassy grain-boundary phase. However, some evidence has also been found for the bonding of individual grains where they come into direct contact across the join line. To investigate the role of grain-boundary phases further, the microwave bonding of two different grades of silicon carbide and one grain of zirconia has been studied. A single-mode resonant cavity operating at 2450 MHz was used for both studies. The temperature and axial pressure were varied and the bonding time was kept to a minimum. Analysis of the resultant bonds indicated that both reaction-bonded silicon carbide and partially stabilized zirconia could be successfully joined using microwave energy with bonding times typically 10 min or less. For reaction-bonded silicon carbide ceramics, the silicon grain-boundary phase softened at the bonding temperature, allowing the butting faces to be "glued" together. Unlike the glassy grain-boundary phase for alumina ceramics, the silicon phase did not allow grain motion but always formed a discrete and continuous layer at the interface, even under optimum joining conditions. The work with zirconia confirmed that it is possible to join ceramics without the presence of a substantial grain-boundary phase. The mechanism is thought to be either solid-state diffusion and/or grain-boundary sliding. © 1998 Kluwer Academic Publishers     

Transformation-toughened zirconia ceramics

Abstract

An assessment has been made of the current interest and potential future of zirconia ceramics for structural applications. Interest in the mechanical properties of ceramics based on, or containing, ZrO₂ centres on the manipulation of the tetragonal to monoclinic martensitic phase transformation. It will be demonstrated that the maintenance of a metastable tetragonal phase is one of the most important factors in the optimum design of a strong and tough ceramic. There are several microstructural approaches that can be taken to achieve toughening based on either precipitate-hardened or particulate-dispersed systems, and a number of different toughening mechanisms can operate, either singly or together, to produce different combinations of properties. The potential engineering future of three ZrO₂ ceramics: partially stabilized zirconia, tetragonal zirconia polycrystals, and zirconia-toughened alumina, is examined in this context. The important relationship between microstructure and mechanical properties is explored for these materials and current applications are cited. The significance of grain boundaries and grain-boundary phases in affecting the way in which the microstructures evolve during sintering and/or aging, and hence in affecting the final properties of the ceramic, are highlighted. The properties of ZrO₂ ceramics in current use are then compared with other common engineering materials, and the problems of property reliability are stated. Finally, an opinion is expressed regarding the deficiency of present scientific effort in ceramics, and some predictions are made concerning the future of ZrO₂ ceramics.

MST/201     

Electronic structure and optical properties of zirconia

The effects of substitutional impurities and oxygen vacancies on the electronic structure and optical properties of cubic zirconia were studied using band-structure calculations. It is shown that oxygen vacancies produce additional states near the Fermi level, whereas impurity atoms make an insignificant contribution to the states in the valence band and at the bottom of the conduction band, and their effect has a predominantly electrostatic character. The mechanisms of the stabilization of the high-temperature ZrO₂ polymorphs are elucidated. The calculation results agree well with x-ray photoelectron spectroscopy and optical data     

Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy

Oxygen vacancy formation and migration in ceria is critical to its electrochemical and catalytic properties in systems for chemical and energy transformation, but its quantification is rather challenging especially at atomic-scale because of disordered distribution. Here we report a rational approach to track oxygen vacancy diffusion in single grains of pure and Sm-doped ceria at −20 °C to 160 °C using in situ (scanning) transmission electron microscopy ((S)TEM). To create a gradient in oxygen vacancy concentration, a small region (∼30 nm in diameter) inside a ceria grain is reduced to the C-type CeO_1.68 phase by the ionization or radiolysis effect of a high-energy electron beam. The evolution in oxygen vacancy concentration is then mapped through lattice expansion measurement using scanning nano-beam diffraction or 4D STEM at a spatial resolution better than 2 nm; this allows direct determination of local oxygen vacancy diffusion coefficients in a very small domain inside pure and Sm-doped ceria at different temperatures. Further, the activation energies for oxygen transport are determined to be 0.59, 0.66, 1.12, and 1.27 eV for pure CeO₂, Ce_0.94Sm_0.06O_1.97, Ce_0.89Sm_0.11O_1.945, and Ce_0.8Sm_0.2O_1.9, respectively, implying that activation energy increases due to impurity scattering. The results are qualitatively supported by density functional theory (DFT) calculations. In addition, our in situ TEM investigation reveals that dislocations impede oxygen vacancy diffusion by absorbing oxygen vacancies from the surrounding areas and pinning them locally. With more oxygen vacancies absorbed, dislocations show extended strain fields with local tensile zone sandwiched between the compressed ones. Therefore, dislocation density should be reduced in order to minimize the resistance to oxygen vacancy diffusion at low temperatures.     

How grain boundaries modify the high-temperature dielectric response of ferroelectric electroceramics like BaTiO3?

Dielectric properties of BaTiO₃ ferroelectric ceramics were studied over wide frequency and temperature ranges. The materials showed complex dielectric behaviors, which included an anomalous increase of permittivity towards higher temperatures. Important, this property tended however to saturate to values that varied with grain-boundary density. Application of impedance spectroscopy and consideration of the series-layer model allowed a coherent discussion of these and other interesting observations from this work. In particular, analysis of the relationship existing in this model between macroscopic and microscopic dielectric properties rendered possible to account for grain vs. grain-boundary dielectric behaviors, in harmony with microstructure features, and to know the dielectric anomaly strength to be in fact expected from grain boundaries in such polycrystalline materials.     

Grain-boundary hardening and elastic recovery of micro-indentations

Variation in micro-hardness across a grain boundary, a well-documented effect found in many materials, is here confirmed for zone-refined iron containing 170 at. ppm of tin. Elastic recovery of the impression-diagonal was practically negligible but considerable recovery occurred in the direction of the indentation penetration depth. The latter is different for impressions located at grain boundaries compared with those located at grain interiors, when small loads are applied; however, this difference diminishes with increasing load. Excess hardening at grain boundaries also decreases as the load increases. The results are discussed in terms of the elastic-plastic properties of the material sampled by the impression, and evaluations of some of the parameters are presented. The correlation between grain-boundary hardening and elastic recovery of the impressions is also indicated.     

Impurity and vacancy segregation at symmetric tilt grain boundaries in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZrO<Subscript>2</Subscript>

Segregation energies of impurity ions and oxygen vacancies at grain boundaries in Y₂O₃-doped ZrO₂ as calculated from atomistic simulations using energy minimization and Monte Carlo methods are reported. Based on these energies, local defect equilibrium concentrations have been estimated. It is found that it is more energetically favorable for an yttrium ion to be accompanied by an oxygen vacancy at grain boundaries, although decrease in energy when associated with an oxygen vacancy differs from boundary to boundary. The segregation energy for a neutral defect complex consisting of a two yttrium ions and an oxygen vacancy at infinitely dilute concentration is highly correlated with the coordination environment of each site in the vicinity of the grain boundary (GB), and, in turn, GB energy. Although the estimated local equilibrium concentrations of these defects are similar, detailed analysis of the atomic coordination and defect distributions in the vicinity of a GB reveal that defect distributions, especially of oxygen vacancies, are dependent on the characteristics of the particular GB and that segregation in effect reduces lattice strains at the GB. Equilibrium concentration distributions of yttrium at grain boundaries are also given as a function of spatial resolution, and are useful for interpretation of experimental results.     

Improvement of creep-rupture properties of wrought cobalt-based HS-21 alloys at high temperatures

The improvement of creep-rupture properties by serrated grain boundaries is investigated using wrought cobalt-based HS-21 alloys in the temperature range 816 to 1038° C (1500 to 1900°F). Serrated grain-boundaries are produced in the early stage of the grain-boundary reaction (GBR) by a heat treatment. Specimens with serrated grain boundaries have superior creep-rupture properties compared with those with normal straight grain boundaries. The rupture lives of specimens with serrated grain boundaries are more than twice as long as those of specimens with straight grain boundaries. The rupture elongation is considerably improved by serrated grain boundaries especially at lower temperatures. A ductile grain-boundary fracture is observed in specimens with serrated grain boundaries, while brittle grain boundary facets prevail in specimens with straight grain boundaries.     

Optical properties of transparent nanocrystalline yttria stabilized zirconia

The optical properties of transparent nanocrystalline zirconia produced using a current activated method were characterized over the entire visible spectrum. The resolutions of the samples were characterized using standard resolution targets. All of the samples produced were found to have as high a resolution as detectable from the test, i.e., they are transparent not translucent. Transmission, reflectance, and absorption coefficients are reported for various wavelengths. The absorption coefficients were found to be highly dependent on processing time. Annealing experiments helped determine that oxygen vacancies (with free electrons) are the primary absorption centers in the visible wavelengths. In addition it was found that grain boundary cores or their associated defects do not contribute significantly to light absorption in the visible range. The lack of an influence of the grain boundary regions is discussed in terms of low oxygen vacancy concentration in the grain boundary space charge layer.     

Impure zirconia electrical conductivity enhancement by rare-earth minority ions in the Y2O3 RE2O3 ZrO2 system

Impure zirconia stabilized by 12 wt% yttria concentrate (85 wt% Y₂O₃ + 15 wt% rare-earth (RE)) was found to have high grain and grain-boundary electrical conductivities. The influence of the RE on the segregation of impurities was studied for four different compositions. Microstructure features are evidence for the enhanced segregation of impurities due to RE ions. The increased grain and grain-boundary conductivities are a consequence of the segregation of impurities.     

Atomic structure of a CeO2 grain boundary: the role of oxygen vacancies

Determining both cation and oxygen sublattices of grain boundaries is essential to understand the properties of oxides. Here, with scanning transmission electron microscopy, electron energy-loss spectroscopy, and first-principles calculations, both the Ce and oxygen sublattices of a (210)Σ5 CeO(2) grain boundary were determined. Oxygen vacancies are shown to play a crucial role in the stable grain boundary structure. This finding paves the way for a comprehensive understanding of grain boundaries through the atomic scale determination of atom and defect locations.     

Y对耐热铝导体材料铸态组织和性能的影响

随着特高压输电技术在我国的大力发展,铝合金导体材料作为特高压输电线路的主要组成部分,受到业内的广泛关注.本文采用电导率测试、硬度测试、金相显微镜和扫描电镜观察等手段,研究添加不同含量稀土Y对铸态Al-Zr耐热铝导体材料的影响.研究结果表明:Y元素和Fe、Si等杂质元素形成金属间化合物,可净化基体,改变杂质相的形态和分布,使其粒子化、球化和细化.Y元素在枝晶网络和晶界分布,从而细化晶粒和枝晶组织,但添加量达到0.5%时晶粒细化不均匀.当Y含量为0.2%时,电导率达到60%IACS;当Y含量为0.3%时,硬度达到最高值20.9HBS,且电导率并无明显下降.加入0.3%Y可使耐热铝导体材料获得较好的综合性能.