The effect of sintering on the grain boundary conductivity of lithium lanthanum titanates

The Li-ion conductivity is a sensitive function of the composition and the microstructure for the perovskite-type Li-ion conductor. In this study, the effect of sintering temperature and thus microstructure and Li loss on the grain boundary conductivity of Li-conducting La_0.57Li_xTiO₃ (x=0.3 and 0.35) were studied. The grain and the grain boundary conductivity were obtained from the impedance patterns. As the sintering temperature increased from 1100°C to 1350°C, the Li content decreased due to the evaporation of Li during sintering. The samples were nearly fully dense after sintering at 1200°C or above. The grain boundary conductivity increased rapidly with sintering temperature due to the increasing grain size. When the grain conductivity was nearly independent on the sintering condition, the grain boundary conductivity change was mostly explained by the microstructural change. Some possible reasons for the low grain boundary conductivity was discussed.     

The effect of surface contact conditions on grain boundary interdiffusion in a semi-infinite bicrystal

The Kirkendall effect is conditioned by active diffusion as well as by active sources and sinks for vacancies. In the case of grain boundaries under the condition of negligible bulk diffusion, the Kirkendall effect is highly localized and responsible for the formation of an extra material wedge in the grain boundary, which may lead to high stress concentrations. The Kirkendall effect in grain boundaries of a binary system is described by a set of partial differential equations for the mole fraction of one of the diffusing components and for the stress component normal to the grain boundary completed with the respective initial and boundary conditions. The contact conditions of the grain boundary with the surface layer acting as source of one of the diffusing components can be considered as equilibrium ones ensuring the continuity of generalized chemical potentials of both diffusing components. Thus, the boundary conditions are determined by the difference in chemistry (i.e. how the thermodynamic parameters depend on chemical composition) of the grain boundaries and of the surface layer. The simulations based on the present model indicate a drastic influence of the chemistry on the grain boundary interdiffusion and Kirkendall effect.     

The relationship between chemical composition distributions and specific grain boundary conductivity in Y-doped BaZrO3 proton conductors

The relationship between chemical composition at a grain boundary and specific grain boundary conductivity is studied in Y-doped BaZrO₃ ceramics sintered at 1800 °C. Y enrichment at the grain boundary as yttrium concentration increased and Ba deficiency in ceramics as an increase of sintering time are observed. At the grain boundary, phase segregation, i.e. existence of secondary phase and amorphous phase which prevent proton migration, is not observed. The results indicate that at the grain boundary, concentration of Ba vacancy and Y substituted into Zr site is changed. Grain boundary conductivity shows significant dependences to Ba deficiency and Y concentration in ceramics. It is due to significant dependences of specific grain boundary conductivity to Ba deficiency and Y concentration in ceramics. The results indicate that proton migration across the grain boundary is sensitive to concentration of those effectively charged defect, i.e. Y substituted into Zr site and Ba vacancy at grain boundary.     

Grain boundary crystallography in polycrystalline yttria-stabilised cubic zirconia

Properties of grain boundaries such as grain boundary energy, mobility and diffusion are reported to depend strongly on their crystallography. While studies on ceramic bicrystals with low Σ misorientations have shown highly ordered structures and low energies, studies on dense polycrystalline ceramics often show the significance of grain boundary planes. In the present study, grain boundary plane distributions were studied for yttria-stabilised cubic zirconia with varying grain sizes using Electron Back Scattered Diffraction technique combined with a stereological approach. Despite nearly isotropic grain boundary plane distributions, a highly anisotropic grain boundary character distribution is observed for specific misorientations. Certain low-energy symmetric tilts such as Σ3 and Σ11 are found to occur with high frequencies across the grain size range studied, leading to an inverse correlation between GB energy and frequency of occurrence, consistent with other ceramics studied in literature.     

Quantifying the grain boundary resistance against slip transfer by experimental combination of geometric and stress approach using stage-I-fatigue cracks

In recent studies, many groups have investigated the interaction of dislocations and grain boundaries by bi-crystals and micro-specimen experiments. Partially, these experiments were combined with supplementary simulations by discrete dislocation dynamics, but quantitative data for the grain boundary resistance against slip transfer is still missing. In this feasibility study with first results, we use stage-I-fatigue cracks as highly localised sources for dislocations with well-known Burgers vectors to study the interaction between dislocations in the plastic zone in front of the crack tip and selected grain boundaries. The stress concentration at the grain boundary is calculated with the dislocation-free zone model of fracture using the dislocation density distribution in the plastic zone from slip trace height profile measurements by atomic force microscopy. The grain boundary resistance values calculated from common geometric models are compared to the local stress distribution at the grain boundaries. Hence, it is possible to quantify the grain boundary resistance and to combine geometric and stress approach for grain boundary resistance against slip transfer to a self-contained concept. As a result, the prediction of the grain boundary resistance effect based on a critical stress concept is possible with knowledge of the geometric parameters of the grain boundary only, namely the orientations of both participating grains and the orientation of the grain boundary plane.     

Effects of boundary inclination and boundary type on shear-driven grain boundary migration

A series of molecular dynamics simulations was performed on a bicrystal to which a fixed shear rate was applied parallel to the boundary plane. Under some conditions, grain boundary motion is coupled to the relative tangential motion of the two grains. In order to investigate the generality of this type of coupled shear/boundary motion, simulations were performed for both special (low Σ) and general (non-Σ) [010] tilt boundaries over a wide range of grain boundary inclinations. The data point to the existence of two critical stresses: one for coupled shear/boundary motion and the other for grain boundary sliding. For the non-Σ boundaries, the critical stress for coupled shear/boundary motion is typically smaller than that for sliding; coupled shear/boundary motion occurs for all inclinations. For Σ5 boundaries, for which the critical stress is smaller and depends on boundary inclination, coupled shear/boundary motion occurs for some, but not all inclinations.     

The influence of grain boundary on the conductivity of donor doped SrTiO3

The electrical conductivity of polycrystalline Sr(Ti_0.999Nb_0.001)O₃ was investigated. The conductivity was smaller by 1–2 order than that of the single crystal. The conductivity increased with temperature with the activation energy of 0.61 eV. The distribution of grain boundary nature of the polycrystalline sample was determined by Orientation Imaging Microscope (OIM) analysis. The ratio of coincident lattice boundaries was determined to be approximately 20%. The impedance of bicrystals across the grain boundary with different grain boundary type was measured. The grain boundary impedance was found to consist of two RC parallel components in series. The activation energies of them were 0.56–0.71 eV and 1.73–1.97 eV, respectively. These two processes were assigned to the grain boundary or annealed surface layer and the Schottky barrier between the bulk and the surface or the grain boundary layer. A possible conduction mechanism of polycrystalline material was considered that of the three dimensional network of the grain boundary layer.     

First-order operators and boundary triples

The aim of the present paper is to introduce a first-order approach to the abstract concept of boundary triples for Laplace operators. Our main application is the Laplace operator on a manifold with boundary; a case in which the ordinary concept of boundary triples does not apply directly. In our first-order approach, we show that we can use the usual boundary operators in abstract Green’s formula as well. Another motivation for the first-order approach is to give an intrinsic definition of the Dirichlet-to-Neumann map and intrinsic norms on the corresponding boundary spaces. We also show how the first-order boundary triples can be used to define a usual boundary triple leading to a Dirac operator. In memoriam Vladimir A. Geyler (1943–2007)     

Thermodynamics and structural aspects of grain boundary segregation

Physical and chemical properties of solid materials are strongly. influenced by the chemical composition of internal interfaces, One of the crucial parameters affecting interfacial chemistry is the atomic structure of the interface. Due to its importance. a considerable amount of work was done to elucidate the relationship between structure and chemical composition of interfaces. This article reviews the present understanding of an important and fundamental part of this relationship, namely, the structural aspects of grain boundary segregation. After a brief outline of grain boundary structure and geometry. thermodynamic approaches to describe grain boundary segregation are summarized and their application to materials is discussed. covering particular sites at a single grain boundary as well as the role of interfaces in polycrystals. Both the experimental evidence of grain boundary segregation anisotropy and the theoretical results of computer simulations of grain boundary segregation are summarized. Useful methods of predicting grain boundary segregation are presented. Finally, segregation behavior of solutes at grain boundaries is compared with that at free surfaces, and examples of chemical composition of intexphase boundaries are given.     

纳晶铜晶粒尺寸对热导率的影响

用热压烧结法制备得到纳晶铜块体. 用激光法测定了不同温度下制备得到的纳晶铜块体的热导率, 并建立卡皮查热阻模型对样品热导率进行模拟. 通过对比, 模拟结果与实验数据基本一致. 随着热压烧结温度的升高, 纳晶铜晶粒尺寸也随之增大. 在900和700 ℃其热导率分别达到了最大和最小值且所对应的热导率分别为200.63和233.37 W·m^-1·K^-1, 各占粗晶铜块体热导率的53.4%和60.6%. 验证了纳晶铜热导率在一定的晶粒尺寸范围内具有尺寸效应, 随着晶粒尺寸的减小, 热导率逐渐减小.     

Theory of grain boundary motion during high-temperature DIGM

A theory of diffusion induced grain boundary migration (DIGM) is presented for high temperatures where volume diffusion of solute atoms out of the grain boundary is important. It is shown that due to the presence of a gradient term in the expression for the free energy of solid solution, even a relatively small discontinuity in the solute distribution across the gain boundary provides enough driving force for grain boundary migration. From the expression obtained for the grain boundary velocity the coefficient for the Ni diffusion across the grain boundaries in a Cu(Ni) polycrystal has been estimated.     

Laser-quality oxide Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> ceramics. Comparative studies of its basic characteristics and laser ceramics of a known manufacturer

The effect of sintering aids of SiO₂, ZrO₂, B₂O₃, and MgO oxides on the optimum sintering temperature, ceramics grain growth, total volume of residual pores, and optical quality of obtained ceramics is studied. The best combinations of sintering aids are found; as a result, YAG:Nd (1 at%) samples of ceramics of high optical quality are obtained. An original method for characterizing laser properties of ceramics is developed. Comparative measurements of main laser characteristics of the obtained ceramics and ceramics of the Konoshima Chemical Corp. Ltd wellknown in the world practice, are performed.     

The boundary of a boundary principle: A unified approach

The boundary of a boundary principle in field theories is described. The difference in treatment of the principle in electrodynamics and general relativity is pointed out and reformulated in terms of underlying mathematical structure of the theories. The problem of unifying the treatment is formulated and solved. The role of E. Cartan's concept of the moment of rotation associated with the curvature of a Levi-Civita connection on a frame bundle is shown to be crucial for the unification. The analysis of the boundary of a boundary principle in Kaluza-Klein theory is performed and the recipe for a unified treatment of the principle in electrodynamics and general relativity is shown to follow from the analysis. It is pointed out that the unification cand be extended to Yang-Mills fields easily.     

Proton-induced grain boundary segregation in stainless steel

Abstract

A technique is developed which addresses the problem of irradiation assisted stress corrosion cracking of stainless steels in light water reactors using high energy protons to induce grain boundary segregation. These results represent the first grain boundary segregation measurements in bulk produced by proton irradiation of stainless steel. The technique allows the study of grain boundary composition with negligible sample activation, short irradiation time, rapid sample turnaround and at minimal cost. Scanning Auger electron microscopy is used to obtain grain boundary composition measurements of irradiated and unirradiated samples of ultra high purity (UHP) type 304L stainless steel and UHP type 304L steels with the additions of phosphorus (UHP + P) and sulphur (UHP + S). Results show that irradiation of all three alloys causes significant Ni segregation to the grain boundary and Cr and Fe away from it. Irradiation of the UHP + P alloy also results in segregation of P at the grain boundary from 5.3 to 8.7 at %, over 80 times the bulk value. No radiation-induced grain boundary segregation of S was measured in the UHP + S alloy. Results also indicate that the presence of P or S may enhance radiation-induced segregation of major alloying elements at the boundary. Comparison of irradiated and unirradiated regions of the UHP + P alloy indicate that while a prior thermal treatment segregates P to the grain boundary to 5.3 at %, the major element concentrations at the grain boundary are completely different from those under irradiation.     

Grain Boundary Kinetics in Oxide Ceramics with the Cubic Fluorite Crystal Structure and its Derivatives

Kinetics of grain boundaries in oxides with the cubic fluorite structure and its derivatives has been investigated using fine grain ceramics that are fully dense. Grain growth measurements in these materials have provided information on grain boundary diffusivity over a diffusion distance of the order of the initial grain size. With the addition of solute cations, grain boundary mobility can be varied over many orders of magnitude, often with very different activation energies. This is caused by the variation of defect population and the defect-solute association. Definitive evidence for solute drag has also been observed in some cases, but solute drag can not be confirmed as a general mechanism in solid solutions. Lastly, while grain boundary at low temperature may continue to serve as a fast diffusion path, it may not be able to migrate because of additional pinning mechanisms such as those exerted by grain boundary nodal points or lines. This means that sintering without grain growth is possible, opening up an avenue for obtaining ultrafine ceramics by pressureless sintering.     

Coarsening in Sintering: Grain Shape Distribution,Grain Size Distribution,and Grain Growth Kinetics in Solid-Pore Systems

Sintering occurs when packed particles are heated to a temperature where there is sufficient atomic motion to grow bonds between the particles. The conditions that induce sintering depend on the material, its melting temperature, particle size, and a host of processing variables. It is common for sintering to produce a dimensional change, typically shrinkage, where the powder compact densifies, leading to significant strengthening. Microstructure coarsening is inherent to sintering, most evident as grain growth, but it is common for pore growth to occur as density increases. During coarsening, the grain structure converges to a self-similar character seen in both the grain shape distribution and grain size distribution. Coarsening behavior during sintering conforms to classic grain growth kinetics, modified to reflect the evolving microstructure. These modifications involve the grain boundary coverage due to pores, liquid films, or second phases and the altered grain boundary mobility due to these phases. The mass transport rates associated with each of these interfaces are different, with different temperature and composition dependencies. Hence, the coarsening rate during sintering is not constant, but changes with the evolving microstructure. Core aspects treated in this review include models for coarsening, grain shape, grain size distribution, and how pores, liquids, dispersoids, and other phases determine microstructure coarsening during sintering.     

Al晶界的第一性原理拉伸试验

基于密度泛函理论和局域密度近似的第一性原理方法，进行了Al晶界的第一性原理拉伸试验.得到Al晶界的理论拉伸强度为9.5 GPa，对应的应变为16%.根据价电荷密度、键长和原子构型随应变的变化，我们证实断裂发生在晶界面，其特征是所有界面键的断裂.同时还发现在周围原子键的数目减少的情况下，界面重构的Al-Al原子键具有共价键的性质.因此Al晶界依然保持着较高的界面强度. 关键词： Al晶界 第一性原理拉伸试验 理论拉伸强度     

包含倾斜晶界的双晶ZnO的热输运行为

用嵌入位错线法和重合位置点阵法构建含有小角度和大角度倾斜角的双晶氧化锌纳米结构.用非平衡分子动力学方法模拟双晶氧化锌在不同倾斜角度下的晶界能、卡皮查热阻,并研究了样本长度和温度对卡皮查热阻和热导率的影响.模拟结果表明,晶界能在小角度区域随倾斜角线性增加,而在大角度区域达到稳定,与卡皮查热阻的变化趋势一致.热导率随样本长度的增加而增加,卡皮查热阻表现出相反的趋势.然而随着温度的增加,热导率和卡皮查热阻都减小.通过比较含5.45°和38.94°晶界样本的声子态密度,发现声子光学支对热传导的影响不大,主要由声子声学支贡献,大角度晶界对声子散射作用更强,声学支波峰向低频率移动.     

Correlation among grain boundary character,carbide precipitation and deformation in Alloy 690

The correlation among grain boundary character, carbide precipitation and deformation in the grain boundary engineering (GBE) treated Alloy 690 samples with and without pre-deformation aged at 715^oC for 15?h was analysed by scanning electron microscopy and electron backscatter diffraction. The fraction of low Σ coincidence site lattice (CSL) grain boundary was enhanced by GBE treatment. The fraction of Σ3 grain boundary decreased, and most of Σ9 and Σ27 grain boundaries disappeared in the deformed GBE samples. After aging treatment, bigger carbide precipitated at coherent Σ3 grain boundary, however, most of plate-like carbide precipitated at incoherent Σ3 grain boundary disappeared in the pre-deformed GBE samples. The larger carbide precipitated on the random grain boundary in the 5% pre-deformed sample, while smaller carbide can be observed in the 15% pre-deformed sample. During the in situ tensile test of the aged GBE samples, grain boundary carbide migrated with the grain boundary migration. The slip bands go across Σ3 grain boundary directly, but cannot go across other grain boundaries. The high density of carbide plate precipitated near incoherent Σ3 and Σ9 grain boundaries can resist the evolution of slip bands. Compared to the Σ3 and Σ9 grain boundaries, Σ27 and random grain boundaries are more easily to form microcrack during deformation. The initiation of grain boundary microcrack not only related to the character of grain boundary but also related to the character of nearby grain boundaries. The phase interface of carbide and matrix is another region to initiate the microcrack.