Effect of Ba6Ti17O40/BaTiO3 Interface Structure on {111} Twin Formation and Abnormal Grain Growth in BaTiO3

A structural transition of Ba₆Ti₁₇O₄₀/BaTiO₃ interfaces from faceted to rough was induced by reducing oxygen partial pressure in the atmosphere. As the oxygen partial pressure decreased, the number densities of {111} twins and abnormal grain decreased. TEM observation showed that the twin formation was governed only by the faceting of the interface. Experimental evidence of {111} twin-assisted abnormal growth of faceted BaTiO₃ grains was also obtained.     

Seeded Growth from Twinned and Untwinned Abnormal Grains of Pb(Mg1/3Nb2/3)O3–35 mol% PbTiO3 in a Matrix Containing PbO Additions

The growth of abnormal grains of PMN–35PT containing Σ3 twin boundaries was compared with that of untwinned abnormal grains of PMN–35PT. It was thought that the twinned abnormal grains might have a growth advantage because of the presence of reentrant edges. The aforementioned types of grains were embedded in a PMN–35PT polycrystalline matrix with 3 vol% excess PbO, and grown by annealing in an oxygen atmosphere at 1150°C for varying times. It was found that abnormal grains containing Σ3 boundaries showed a comparable degree of growth to that of the untwinned grains. Furthermore, for the twinned seed crystals, the extent of growth was independent of whether there was any initial entrapped porosity within the abnormal grain.     

Direct Synthesis and Hydration of Calcium Aluminosulfate (Ca4Al6O16S)

Calcium aluminosulfate (Ca₄Al₆O₁₆S or C₄A₃̄) was prepared by direct synthesis from calcium and aluminum nitrates, and aluminum sulfate. CaAl₄O₇(CA₂) formed as an intermediate at 900°C, and C₄A₃̄ was the main phase after calcination at 1100°C. The specific surface areas after calcination at 1100° and 1300°C were ∼2.5 and 1 m²/g, respectively. Hydration was investigated using XRD, DSC, SEM, conduction calorimetry, and solid-state ²⁷Al MAS-NMR spectroscopy. Calorimetry showed that the induction period was longer than that of a sample prepared using conventional solid-state sintering, and this was attributed to the formation of amorphous coatings. Crystalline hydration products, principally calcium monoaluminosulfate hydrate and aluminum hydroxide, appeared subsequently. Although the induction period was very long, complete hydration occurred as early as 3 d in the sample calcined at 1100°C and was 91% complete in the sample calcined at 1300°C.     

Hydration of Beta Dicalcium Silicate Alone and in the Presence of CaCl2 or C2H5OH

Beta C₂S was hydrated at room temperature with and without added CaCl₂ or C₂H₅OH by methods previously studied for the hydration of C₃S, i.e. paste, bottle, and ball-mill hydration. The amount of reacted β-C₂S, the Ca(OH)₂ concentration in the liquid phase, the CaO/SiO₂ molar ratio, and the specific surface area of the hydrate were investigated. A topochemical reaction occurs between water and β-C₂S, resulting in the appearance of solid Ca(OH)₂ and a hydrated silicate with a CaO/SiO₂ molar ratio of ≃1. As the liquid phase becomes richer in Ca(OH)₂, the first hydrate transforms to one with a higher CaO/SiO₂ ratio. Addition of CaCl₂ increases the reaction rate and the surface area of the hydrate but to a much lesser extent than in the hydration of C₃S, whereas C₂H₆OH strongly depresses the hydration rate of β-C₂S, as observed for C₃S hydration.     

Shape of MgAl2O4 Grains in a CaMgSiAlO Glass Matrix

When sintered Al₂O₃ is annealed with CaMgSiAlO glass at 1600°C, polyhedral MgAl₂O₄ grains form and glass pockets are entrapped within the grains. After annealing for 13 h at 1600°C, the liquid pockets show a regular octahedron shape which is expected to represent the equilibrium shape. All grain surfaces in contact with the glass matrix show the same shape. The small grains, which must be shrinking, thus have the equilibrium shape, because their shrinkage shape is is identical to the equilibrium and growth shape. However, the octahedral shape also represents the growth shape for the growing large grains. The grains also form grain boundaries with neighboring grains.     

Kinetics of Templated Grain Growth of 0.65Pb(Mg1/3Nb2/3)O3·0.35PbTiO3

Single-crystal layers of 0.65Pb(Mg_1/3Nb_2/3)O₃·0.35PbTiO₃ (PMN-35PT) were grown heteroepitaxially on {001}-BaTiO₃ template crystals. A {001}-BaTiO₃ crystal was embedded in a fine-grained matrix of PMN-35PT containing excess PbO and heated between 950° and 1150°C for 0–5 h. The initial growth of the PMN-35PT on the {001} surface and the growth of the matrix grains both displayed a t ^1/3 dependence which is characteristic of diffusion-controlled growth. Growth was limited to ∼100–150 μm due to the significantly reduced driving force at longer times because of matrix coarsening and porosity evolution.     

Effect of Li2O and PbO Additions on Abnormal Grain Growth in the Pb(Mg1/3Nb2/3)O3–35 mol% PbTiO3 System

Abnormal grain growth in Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ (PMN-35PT) ceramics doped with Li₂O and PbO has been investigated. Replacing the PbO dopant with up to 2 mol% Li₂O caused an increase in the number of abnormal grains. For the composition containing 2 mol% Li₂O and 6 mol% PbO, the amount of abnormal grain growth decreased with increasing sintering temperature. Single crystals of ∼6 mm × 6 mm × 2 mm thickness were grown from the 2 mol% Li₂O, 6 mol% PbO-containing composition via the templated grain growth method. Grain growth behavior with temperature is explained in terms of the effect of Li₂O on interface-reaction-controlled grain growth and the critical driving force.     

Effect of Grain Coalescence on the Abnormal Grain Growth of Pb(Mg1/3Nb2/3)O3-35 mol% PbTiO3 Ceramics

Abnormal grain growth (AGG), which occurred during the heat treatment of Pb(Mg_1/3Nb_2/3)O₃-35 mol% PbTiO₃ (PMN-35PT) with excess PbO, was investigated. AGG has been suggested to be the consequence of grain coalescence that results in the formation of Σ3 coincidence site lattice and low angle grain boundaries. Because of reentrant edges appearing at the ends of these boundaries, the coarsening rate of grains was significantly enhanced and AGG occurred.     

Abnormal Grain Growth of Pb(Mg1/3Nb2/3)O3-35 mol% PbTiO3 Ceramics Induced by the Penetration Twin

Pb(Mg_1/3Nb_2/3)O₃-35 mol% PbTiO₃ (PMN-35PT) specimens with a 5 mol% excess PbO were prepared by excessive heat treatment at 1150°C to induce abnormal grain growth. Through electron backscatter diffraction analysis and the observation of a three-dimensional morphology, the abnormally grown PMN-35PT grains were found to be twinned crystals with penetration characteristics. The morphology of the PMN-35PT twinned crystal was crystallographically analyzed. The abnormal grain growth of PMN-35PT is suggested to be due to preferential growth at the reentrant angles formed by twins.     

Rapid Formation and Growth of Bixbyite-Type (In0.67Fe0.33)2O3 by 28 GHz Microwave Irradiation

(In_0.67Fe_0.33)₂O₃ with the bixbyite structure was synthesized via 28 GHz microwave irradiation, using multimode microwave heating equipment. Indium sesquioxide strongly absorbs 28 GHz microwaves, and this strong coupling with microwave energy can be used to drive a reaction with iron sesquioxide. A mixture of In₂O₃ and α-Fe₂O₃ powders (In:Fe ratio of 2:1) was irradiated with microwaves at a frequency of 28 GHz. The mixture was heated to 1400°C during the microwave irradiation. The formation of a solid solution was completed within a minute, which indicated a drastic enhancement of the reaction rate. Scanning electron microscopy revealed remarkable grain growth under microwave irradiation.     

Mechanism for the Peritectic Reaction and Growth of Aligned Grains in YBa2Cu3O6+x

It is experimentally observed that the peritectic reaction, 211 + liquid → 123, can be driven essentially to completion in 1 h at an undercooling of only ∽30°C. The kinetic data, together with the observed microstructures, are inconsistent with the normal mechanism of the peritectic reaction. It is proposed that the mechanism of the reaction involves dissolution of 211 particles into the liquid and precipitation of solid 123. The aligned grain structure is explained through sympathetic nucleation of new 123 grains on existing grains.     

C70 Nanowhiskers Fabricated by Forming Liquid/Liquid Interfaces in the Systems of Toluene Solution of C70 and Isopropyl Alcohol

C₇₀ whiskers with submicrometer diameters (C₇₀ nanowhiskers, or C₇₀NWs) have been successfully fabricated by forming liquid/liquid interfaces in systems that involve a toluene solution of C₇₀ and isopropyl alcohol. Transmission electron microscopy observations show that the C₇₀NWs have a 〈110〉 growth axis and that the intercluster distance of C₇₀ molecules in the C₇₀NWs are shortened by ∼3%, compared with that of face-centered cubic C₇₀ crystals in the 〈110〉 close-packed growth direction, which indicates the formation of strong chemical bonds between the C₇₀ molecules. It is suggested that the C₇₀ molecules are polymerized, with their short axis parallel to the growth axis of the C₇₀NWs, from observation via high-resolution transmission electron microscopy.     

Reactive-Templated Grain Growth of Bi1/2(Na,K)1/2TiO3: Effects of Formulation on Texture Development

In this paper we report the effects of formulation on texture development for the "reactive-templated grain growth" (RTGG) of Bi_1/2(Na,K)_1/2TiO₃ (BNKT). The solids formulation for BNKT was systematically varied by prereacting to well—defined alkali and bismuth titanates (Na₂Ti₃O₇ (N₂T₃), K₂Ti₂O₅ (K₂T₂), and Bi₂Ti₄O₁₁ (B₂T₄)). Use of these precursors in different BNKT formulations determined that the amount of expansion associated with reacting dry-pressed compacts at 600−800°C could be influenced by formulation. Lotgering factors ( F _{00 l} ) derived from Θ/2Θ X-ray diffraction scans indicated that the formulation route strongly affected the {00 l } texture development in tape-cast and sintered specimens. Prereacting alkali carbonates with TiO₂ to form N₂T₃ and K₂T₂ inhibited texture development in RTGG-processsed BNKT. However, when Bi₂O₃ was prereacted to form B₂T₄, the measured F _{00 l} increased from 0.5 to 0.7.     

Growth of BaTiO3 Seed Grains by the Twin-Plane Reentrant Edge Mechanism

Two different types of BaTiO₃ seed particles, normal and twinned seeds of ∼30 μm on the average, were prepared from crushed sintered specimens. Normal seeds were obtained from the usual BaTiO₃ sintered compacts, while twinned seeds containing a double twin were obtained from BaTiO₃ compacts sintered with 2 mol% of SiO₂. The BaTiO₃ powder compacts were again prepared with 5 wt% of seed grains and sintered under various conditions. The microstructural evolution was quite different in the two cases: the growth of normal seed grains was ultimately limited but that of the twinned seeds continued extensively. The observed difference is discussed in terms of the growth mechanism and the atomic structure of interfaces.     

Changes in Zeta Potential During Hydration of C3S With and Without CaCl2 Additions

C₃S and C₃S+2% CaCl₂ were hydrated for varied times; the degree of hydration and zeta potential were determined. In the absence of CaCl₂, the duration of the induction period was 5 h, whereas when CaCl₂ was added, an induction period of 1 h was observed. The zeta potential was positive, maximum, and constant during induction .     

Retention of Cobalt, Cesium, and Strontium in the Hydrates of C3S, C3A, and Gypsum

The retention of cobalt, cesium, and strontium as trace elements in the hydrates of simple ordinary portland cement components has been investigated. The combined characterization of the solid by SEM, electron microprobe, XRD, and SIMS, as well as the chemical analysis of the solutions, allowed us to identify the likely localization of these trace elements in the solid. In particular, cobalt is dramatically incorporated into the solid during the hydration of C₃S; we show that this is due to the formation of a cobalt oxychloride, a compound which is unstable at temperatures ≥60°C. Cesium is retained in small amounts in the C-S-H and CH mixture. The formation of hydrated aluminates notably increases its retention. Finally, small quantities of strontium are also retained in silicates and, in the presence of gypsum, its retention is markedly higher. This is likely due to the formation of sulfoaluminates.     

Control of Grain-Boundary Pinning in Al2O3/ZrO2 Composites with Ce3+/Ce4+ Doping

The control of the microstructure of Ce-doped Al₂O₃/ZrO₂ componsites by the valence change of cerium ion has been demonstrated. Two distinctively different types of microstructure, large Al₂O₃ grains with intragranular ZrO₂ particles and small Al₂O₃ grains with intergranular ZrO₂ particles, can be obtained under identical presintering processing conditions. At doping levels greater than ∼ 3 mol% with respect to ZrO₂, Ce³⁺ raises the alumina grain-boundary to zirconia particle mobility ratio. This causes the breakaway of grain boundary from particles and the first type of microstructure. On the other hand, Ce⁴⁺ causes no breakaway and produces a normal intergranular ZrO₂ distribution. The dramatic effect of Ce³⁺ on the relative mobility ratio is found to be associated with fluxing of the glassy boundary phase and is likewise observed for other large trivalent cation dopants. The ZrO₂ second phase acts as a scavenger for these trivalent cations, provided their solubility limit in ZrO₂ is not exceeded.     

Microstructural Development in SnO2-Doped ZnO–Bi2O3 Ceramics

The effects of adding small quantities of SnO₂ to the basic ZnO–Bi₂O₃ varistor composition were studied in terms of phase reactions, microstructural development, and the formation of inversion boundaries. Scanning and transmission electron microscopy studies showed that the inversion boundaries, triggered by the addition of SnO₂, cause anisotropic grain growth in the early stages of sintering. ZnO grains that include inversion boundaries grow exaggeratedly, at the expense of normal grains, until they dominate the microstructure. Higher additions of SnO₂ lead to an increase in number of grains with inversion boundaries and to a more fine-grained microstructure. The increasing amount of secondary phases is also related to a higher level of SnO₂ addition; however, the influence of these phases on ZnO grain growth is subordinate to the role of inversion boundaries.     

Hydration Study of the System Ca3Al2O6–CaSO4· 2H2O–Ca(OH)2–H2O with and without Citric Acid

Hydration occurring in the system Ca₃Al₂O₆–CaSO₄· 2H₂O–Ca(OH)₂–H₂O has been studied at different temperatures and it was found that the reactions are diffusion controlled. The kinetic data obeyed Jander's equation and the rate of reaction increased with increasing temperature. X-ray diffraction studies and calorimetric measurements show that when gypsum is consumed, ettringite is converted into monosulfate. The rate of this conversion also increased with the increasing temperature and decreased in the presence of citric acid. Spectroscopic studies showed that there was some interaction between citric acid and the cement and that the product of hydration is of colloidal nature. Zeta potential measurements show that retardation of Ca₃Al₂O₆ hydration in the presence of gypsum and Ca(OH)₂ is not due to SO²⁻₄ adsorption. Electrical conductivity and thermoelectric potential measurements of solid Ca₃Al₂O₆ show that Ca₃Al₂O₆ is an n -type semiconductor and contains defects. The retardation of Ca₃Al₂O₆ may be due to poisoning of reaction sites by gypsum and Ca(OH)_2.