Singular Grain Boundaries in Alumina and Their Roughening Transition

The shapes and structures of grain boundaries formed between the basal (0001) surface of large alumina grains and randomly oriented small alumina grains are shown to depend on the additions of SiO₂, CaO, and MgO. If a sapphire crystal is sintered at 1620°C in contact with high-purity alumina powder, the grain boundaries formed between the (0001) sapphire surface and the small alumina grains are curved and do not show any hill-and-valley structure when observed under transmission electron microscopy (TEM). These observations indicate that the grain boundaries are atomically rough. When 100 ppm (by mole) of SiO₂ and 50 ppm of CaO are added, the (0001) surfaces of the single crystal and the elongated abnormal grains form flat grain boundaries with most of the fine matrix grains as observed at all scales including high-resolution TEM. These grain boundaries, which maintain their flat shape even at the triple junctions, are possible if and only if they are singular corresponding to cusps in the polar plots of the grain boundary energy as a function of the grain boundary normal. When MgO is added to the specimen containing SiO₂ and CaO, the flat (0001) grain boundaries become curved at all scales of observation, indicating that they are atomically rough. The grain boundaries between small matrix grains also become defaceted and hence atomically rough.     

Faceting of High-Angle Grain Boundaries in Titanium-Excess BaTiO3

The grain boundaries in BaTiO₃ with excess Ti of 0.5, 0.3, and 0.1 at.% sintered at 1300° or 1250°C have been examined by scanning electron microscopy (SEM), electron backscattered diffraction pattern (EBSP), and transmission electron microscopy (TEM). In the 0.1% Ti-excess specimen, large grains growing abnormally form high-angle grain boundaries when they impinge on each other as verified by EBSP. A large fraction of these grain boundaries are faceted with hill-and-valley shapes. In the 0.5% Ti-excess specimen, large grains growing abnormally are elongated in the directions of their {111} double twins. These grains often form flat grain boundaries parallel to their {111} planes with the fine matrix grains, and the grain-boundary segments between the large impinging grains with high misorientation angles are often also parallel to the {111} planes of one of the grains. These grain boundaries are expected to be singular. Most of the grain boundaries between the randomly oriented fine-matrix grains in the 0.3 at.% Ti-excess specimen are also faceted with hill-and-valley shapes at finer scales when observed under TEM. The facet planes are parallel to {111}, {011}, and {012} planes of one of the grain pairs and are also expected to be singular. These high-angle grain boundaries lying on low index planes of one of the grain pairs are similar to those observed in other oxides and metals.     

Effect of Interface Structure on the Microstructural Evolution of Ceramics

The interface atomic structure was proposed to have a critical effect on microstructure evolution during sintering of ceramic materials. In liquid-phase sintering, spherical grains show normal grain growth behavior without exception, while angular grains often grow abnormally. The coarsening process of spherical grains with a disordered or rough interface atomic structure is diffusion-controlled, because there is little energy barrier for atomic attachments. On the other hand, kink-generating sources such as screw dislocations or two-dimensional (2-D) nuclei are required for angular grains having an ordered or singular interface structure. Coarsening of angular grains based on a 2-D nucleation mechanism could explain the abnormal grain growth behavior. It was also proposed that a densification process is closely related to the interface atomic structure. Enhanced densification by carefully chosen additives during solid state sintering was explained in terms of the grain-boundary structural transition from an ordered to a disordered open structure.     

Surface Roughening Transition and Coarsening of NbC Grains in Liquid Cobalt-Rich Matrix

When NbC–30 wt% Co powder compact is sintered at various temperatures where NbC grains (with small amounts of Co) coexist with a liquid Co–NbC matrix, the NbC grains undergo a surface roughening transition with temperature increase and the grain growth changes from abnormal to normal growth. When sintered at 1400°C, the grains are polyhedral with sharp edges (and corners) and grow abnormally because their singular surfaces move by nucleation of surface steps. When sintered at 1600°C, the edges become round, indicating the surface roughening transition. The grains still grow abnormally, but their number density is larger than that at 1400°C because of the smaller surface step free energy. When sintered at 1820°C, the grains are nearly spherical, but the flat-surface segments still remain. The grain growth at this temperature is nearly normal because of very small surface step free energy. The surface roughening transition is reversed when a specimen initially sintered at 1820°C is heat-treated again at 1400°C, but some grains show transition shapes with nearly flat edges and slope discontinuities (shocks).     

Grain size dependence of hardness in nanocrystalline silicon carbide

The response of nanocrystalline silicon carbide (nc-SiC) to nanoindentation is investigated using molecular dynamics (MD) simulation. It is found that the hardness of the nc-SiC decreases with decreasing grain size, showing an inverse Hall-Petch relationship. The behavior is primarily attributed to the reduced number of intact covalent bonds with grain refinement. Dislocation nucleation and growth in nc-SiC are strongly suppressed by the grain boundaries (GBs). In addition to the dislocation region in the grains, the indentation-induced amorphization of nanograins proceeds preferentially from the GBs, leading to grain shrinkage until the grains are fully amorphized. The results provide an improved understanding of the mechanical properties in nc-SiC and other nanostructured covalent materials.     

Impedance Spectroscopy of Undoped BaTiO3 Ceramics

The electrical properties of ceramic BaTiO₃ were investigated by ac impedance spectroscopy over the ranges 25°-330°C and 0.03 Hz-1 MHz. Results are compared with those obtained from fixed-frequency measurements, at 1 kHz and 100 kHz. Fixed-frequency Curie-Weiss plots show deviations from linearity at temperatures well above t _c. The ac measurements show that grain boundary impedances influence Curie-Weiss plots in two ways: at high temperatures, they increasingly dominate the fixed-frequency permittivities; at lower temperatures, closer to T ^c, the high-frequency permittivity contains a contribution from grain boundary effects. Methods for extraction of bulk and grain boundary capacitances from permittivity and electric modulus complex plane plots are discussed. The importance of selecting the appropriate equivalent circuit to model the impedance response is stressed. A constriction impedance model for the grain boundary in BaTiO₃ ceramics is proposed: the grain boundary capacitance is neither temperature-independent, nor shows Curie-Weiss behavior. The grain boundary is ferroelectric, similar to the grains, but its impedance is modified by either air gaps or high-impedance electrical inhomogeneity in the region of the necks between grains; the activation energy of the constriction grain boundary impedance differs from that of the bulk, suggesting differences in defect states or impurity levels.     

Habits of Grains in Dense Polycrystalline Solids

We show here that the boundaries of individual grains in dense polycrystals prefer certain crystallographic habit planes, almost as if they were independent of the neighboring crystals. In MgO, SrTiO₃, MgAl₂O₄, TiO₂, and aluminum, the specific habit planes within the polycrystal correspond to the same planes that dominate the external growth forms and equilibrium shapes of isolated crystals of the same phase. The observations decrease the apparent complexity of interfacial networks and suggest that the mechanisms of solid-state grain growth may be analogous to conventional crystal growth. The results also indicate that a model for grain-boundary energy and structure based on grain surface relationships is more appropriate than the widely accepted models based on lattice orientation relationships.     

Coarsening Behavior of Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) Grains Dispersed in a Clinker Melt

Microstructural evolution during the heat treatment of cement clinker was investigated. Two model specimens, which consisted of faceted tricalcium silicate (C₃S) and spherical dicalcium silicate (C₂S) grains dispersed in a liquid matrix, were prepared with 5 wt% of large seed particles. The seed particles of faceted C₃S grains grew extensively, whereas those of the spherical C₂S grains grew rather slowly, relative to the matrix grains. As a consequence, C₃S grains exhibited a bimodal size distribution that was typical of exaggerated grain growth, whereas C₂S grains retained a uniform and normal size distribution. These results suggest that the growth of faceted C₃S grains was controlled by the interface atomic attachment, such as two-dimensional nucleation, and that of spherical C₂S grains was controlled by diffusion through the liquid matrix. The dependence of growth mechanisms on grain morphology has been explained in terms of the atomistic structure of the solid/liquid interface.     

Facet–Defacet Transition of Grain Boundaries in Alumina

Grain boundaries in pure alumina powder compacts sintered at 1400°C are smoothly curved, indicating that they have atomically rough structures. When these specimens are heat-treated at temperatures between 900° and 1100°C, a small fraction of the grain boundaries develop either hill-and-valley or kinked shapes with flat segments. Some of these flat boundary segments lie on the {011[Twomacr]} plane of one of the grain pairs. These grain boundaries thus appear to become singular at these temperatures. When a corundum crystal with a basal surface is sintered in alumina powder at 1400°C, all grain boundaries formed between the corundum basal surface and small grains, as well as those between the small grains, are smoothly curved, indicating their rough structure. When heat-treated at 900°C for 3 days, about 30% of the grain boundaries between the corundum basal surface and the small grains develop kinks with flat boundary segments, and some of these flat segments lie on the basal plane of the corundum. When heat-treated again at 1400°C, all grain boundaries are curved, indicating that they become reversibly rough. These observations show that at least some of the grain boundaries in alumina undergo roughening-singular transitions at temperatures between 900° and 1100°C.     

Abnormal Grain Growth in Alumina with Anorthite Liquid and the Effect of MgO Addition

Abnormal grain growth (AGG) in alumina with anorthite liquid has been observed with varying anorthite and MgO contents, at 1620°C. When only anorthite is added to form a liquid matrix, the grain–liquid interfaces have either flat or hill-and-valley shapes indicating atomically flat (singular) structures. The large grains grow at accelerated rates to produce AGG structures with large grains elongated along their basal planes. This is consistent with the slow growth at low driving forces and accelerated growth above a critical driving force predicted by the two-dimensional nucleation theory of surface steps. With increasing temperature, the AGG rate increases. The number density of the abnormally large grains increases with increasing anorthite content. The addition of MgO causes some grain–liquid interfaces to become curved and hence atomically rough. The grains also become nearly equiaxed. With increasing MgO content the number density of the abnormally large grains increases until the grain growth resembles normal growth. This result is qualitatively consistent with the decreasing surface step free energy associated with partial interface roughening transition.     

Analysis of one dimensional grain model

Model equations for slab type pellet consisting of spherical grains are solved numerically. It is shown that some of the generalised equations reported in the literature for slab type pellets with slab type grains and spherical pellets with spherical and slab type grains are equally applicable to a slab type pellet with spherical grains. A sensitivity analysis of the model to various parametric changes has been made and compared with experimental data on zinc sulphide oxidation to indicate the significance of the various assumptions. It is also shown that the model can be extended to solid-consuming reactions as well. Experimental results on gasification of carbon with carbon dioxide reported in the literature were verified satisfactorily with the present model equations.     

Grain coalescence in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C during spark plasma sintering

High-entropy (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C ceramics (HEC) are fabricated via spark plasma sintering using different die configurations, including the conductive and insulating dies. Compared to the conductive die, the grain sizes of samples sintered in the insulating die are significantly larger, which is attributed to the higher local temperature as a result of the higher current density in the sample. Furthermore, the microstructure evolution and grain growth mechanism of HEC are investigated for the first time. We find that at moderate temperatures (∼1600°C), the grain growth of HEC can occur by a grain coalescence mechanism, forming numerous irregular grains in the porous sample. Three factors are crucial to induce grain coalescence, including the formation of partial melting layers on particle surfaces, nanograin rearrangement via rotation and sliding, and the formation of low-angle grain boundaries. During the final sintering stage, the irregular grains will change into polyhedral shapes by grain boundary migration. These findings are of assistance to better understand and control the microstructure evolution of HEC and other ultrahigh-temperature carbide ceramics.     

Grain Boundary Sliding Microdisplacement Measurements During the Creep of Alumina

Grain boundary sliding (GBS) is thought to be the principal driving force for the nucleation, growth, and coalescence of grain boundary cavities during compressive creep of polycrystalline ceramics. It has been shown theoretically that stochastic GBS gives rise to continuous cavity nucleation and transient cavity growth and coalescence, eventually leading to crack formation and failure. This paper will show through experimental measurements, using stereoimaging techniques, that GBS is in fact stochastic. Also, mode II GBS, in-plane grain rotation, and in-grain shear displacements, strains, and strain rate measurements during creep of Lucalox Al₂O₃ will be presented. These displacements, measured on a machine vision system, will be presented in terms of the surrounding microstructural constraint and their lack of angular relation to the compressive load axis.     

Microstructure and Composition of Primary and Recycled Single Grains of YBCO,GdBCO‐Ag,and SmBCO‐Ag Bulk Superconductors

The widespread use of single grain RE‐Ba‐Cu‐O [(RE)BCO] bulk superconductors, where RE is typically Sm, Gd, or Y, is, in part, limited by the relatively high costs of precursor powders and the low success rate of the manufacturing process. Both these problems can be addressed by recycling primary‐processed grains in which the initial growth process has failed in some way. Key to the use of recycled grains in practical applications is an assurance that their properties and performance are not inferior to those of primary grown grains. In this work, we describe the differences between the growth process, microstructure, and properties of primary and recycled (RE)BCO single grains. We observe that the mechanism of growth is the same for both primary and recycled single grain samples in all three RE‐based systems investigated. In the recycling process additional liquid‐rich phase powder is provided beneath a failed sample, whereby this liquid phase infiltrates upwards and contributes a sufficient concentration of additional RE species at the growth front to enable samples to grow relatively easily in the form of single grains by producing a more uniform composition at the growth front, which leads directly to an increased tolerance to the presence of Ag and Ce‐rich agglomerates. Importantly, we observe that the recycled samples have a much more uniform composition, and therefore exhibit more uniform superconducting properties, than single grain samples fabricated by a primary grown process.     

Bi-templated grain growth maximizing the effects of texture on piezoelectricity

Templated grain growth is beneficial for piezoelectric materials, the properties of which become the best in their single crystalline form. Nevertheless, a textured ceramic prepared by a templated grain growth technique often fails in exhibiting as good properties as expected in single crystals even with a high degree of orientation factor. Here, we propose a new strategy for maximizing texturing effect by suppressing the growth of untextured matrix grains. The textured ceramics made by our method, so-called bi-templated grain growth, are featured by ultrahigh piezoelectric properties (d₃₃ = ～1,031 pC/N, d?g = ～59,000, k_p = ～0.76). A special emphasis is on the achieved electric-field-induced strain of 0.13 % at 1 kV/mm, which is as high as that of single crystals. This work demonstrates that not only the degree of texture but also the coarsening of untextured matrix grains should be well-controlled to best exploit the templated grain growth technique.     

Forces between Aluminum Oxide Grains in a Silicate Melt and Their Effect on Grain Boundary Wetting

Experiments in which the disperson and flocculation behavior of aluminum oxide grains in a Ca-Al-Si-O silicate liquid are examined have been used to determine the nature of the forces between oxide grains in a silicate melt. From observations of the way in which the melt penetrates grain boundaries in a high-purity polycrystalline aluminum oxide, it is concluded that at short ranges the interaction between most grains is strongly repulsive. The formation of aggregated groups of grains in settling experiments, however, indicates that at larger separations the forces between grains become attractive and hence that there is an energetic minimum in the interaction between grains. The results are discussed in relation to models for the stability of intergranular films in liquid-phase-sintered ceramics. Microstructural observations made on the melt-penetrated aluminas are used to make a quantitative estimate of the fraction of grain boundaries that are wetted by the melt. The observations indicate that large clusters of grains connected by unwetted grain boundaries exist in liquid-phase-sintered aluminas.     

NATURAL CONVECTION EFFECTS IN STORED GRAINS -A SIMULATION STUDY

ABSTRACT

A two-dimensional time-dependent numerical model has been developed to study heat and moisture transfer by natural convection in piles of grain. Results have been obtained for a rectangular storage bin with and without a headspace, and a bunker-type storage structure. Contour plots of streamlines, isotherms, velocity vectors and grain moisture content show the effects of natural convection and of fluctuating thermal boundary conditions on the stored grains. The numerical solution also offers an insight into the underlying physical mechanisms of the moisture redistribution in grain bulks.     

Controlled synthesis of anatase/tungstite heterogeneous nanomaterials induced by oxalic acid

A series of anatase/tungstite heterogeneous nanomaterials with various molar ratios were synthesized by hydrothermal method with oxalic acid as additive, in which the nucleation and growth of tungstite grains were controlled effectively. In our experiments, tungstite grains grew on the surface of TiO₂ grains, which was significant for obtaining heterogeneous composites, and the grain boundaries in composites were considered to promote photocatalytic ability effectively. It was demonstrated that heterogeneous nanomaterials synthesized had obviously better photocatalytic ability than the physical mixture of homogeneous nanomaterials (pure anatase and tungstite) no matter if under ultraviolet irradiation or visible light.     

大颗粒瓷质砖新型湿法造粒工艺设备的研究

为增强抛光砖表面大颗粒的仿石效果和建筑装饰效果,采取在同一颗粒中产生径向多色层和具有多种色泽的复合造粒工艺,颗粒形状除片状、角状外,还有不规则的球状,使颗粒形态各异、色彩斑斓;通过该工艺还能提高颗粒的边缘结合能力,改善压制成形性能,提高抛光加工合格率。为此我们设计了一种新型的瓷质砖大颗粒成套湿法造粒设备,它包括配料、加水自动控制系统、预混合系统、初级造粒、造粒系统。     

Singular Grain Boundaries in Alumina Doped with Silica

Pure Al₂O₃ powder compact sintered at 1400°C after adding 100 mol ppm of SiO₂ shows grain boundaries that are flat, even across the triple junctions. TEM observations show that these flat grain boundaries are parallel to the basal planes of the grains on one side. These flat grain boundaries must be singular. At such a low SiO₂ concentration and a low temperature, it is very unlikely that any liquid phase is present at these grain boundaries to cause such flat boundary shapes.