Templated Grain Growth of Textured Bismuth Titanate

Textured bismuth titanate, Bi₄Ti₃O₁₂ (BiT), was produced by templated grain growth (TGG). Molten-salt-synthesized BiT platelets were dispersed in a matrix of 200 nm BiT powder and aligned by tape casting. Highly textured BiT was obtained with the use of only 5 vol% template particles by sintering at 1000°C for 1 h. The uniformity of the through-thickness texture is much higher than reported in the literature for BiT tapes cast with 100% platelets. Initial platelet alignment is shown to increase because of frequent interaction with the fine powder particles during tape casting. By avoiding pressure densification techniques and using only a small portion of anisometric particles, TGG is a low-cost option for fabricating textured ceramics.     

Development of Textured Mullite by Templated Grain Growth

Highly textured mullite was obtained by enhancing anisotropic grain growth by TiO₂ doping and by templating grain growth on oriented acicular mullite seed particles in a mullite precursor. Upon heating, the mullite precursor crystallized and densified to an equiaxed microstructure of 1-2 µm mullite grains at which time the mullite seed particles grew rapidly in the length direction ( c -axis) to produce a highly textured microstructure. By changing the seed (template) particle concentration, a range of oriented microstructures and anisotropic grains could be produced.     

Reaction-based Processing of Textured Alumina by Templated Grain Growth

Highly textured, dense alumina ceramics were fabricated by a new processing route which utilizes a mixture of Al metal powder, alumina powder, alumina platelet (template) particles and a liquid phase former. The process involves dry forming the powder mixture (e.g. uniaxial pressing, and roll compaction) to align the plate-like template particles. The addition of a calcium aluminosilicate glass reduces constrained densification by the template particles and allows attainment of high density at ∼1450°C. The degree of orientation (i.e. r is 1 for a random sample and 0 for a perfectly textured material) and volume fraction of textured material, f, were measured by X-ray-based rocking curve technique and SEM-based stereological analysis, respectively. It has been shown that texture quality (the r parameter) is controlled by initial strain during forming, sintering time and temperature. In addition, alumina ceramics with the volume fraction of textured material ranging from 1 to ∼100% can be obtained.     

Critical Factors in the Templated Grain Growth of Textured Reaction-Bonded Alumina

The Templated Grain Growth (TGG) of Al₂O₃ occurs in three stages: densification, radial growth of individual template grains until template impingement, and template grain thickening. Significant template growth occurs only after densification to ∼90% density. Template loading determines the inter-template spacing and, subsequently, the degree of growth. The spacing distance can be predicted from the initial template concentration and template dimensions. Thermodynamic conditions favorable for template growth occur when the size ratio between the template thickness and matrix grains is ≥1.5. The initial template concentration should be less than a critical template concentration, V _T,C, to achieve textured ceramics with a narrow orientation distribution. For this system, which uses 20 ± 5 μm × 2 μm template particles and uniaxial pressing as a forming technique, V _T,C is between 5 and 10 vol%.     

Fabrication of Highly Textured Fine‐Grained α‐Alumina by Templated Grain Growth of Nanoscale Precursors

[0001] textured alumina ceramics with a fine grain size were fabricated between 1400°C and 1600°C via templated grain growth (TGG) using fine alumina platelets (~0.6 and ~3 μm diameter) aligned by tape casting in either a 50 nm α‐Al₂O₃ matrix powder, or in a seeded boehmite sol. The 3 μm templates could be readily aligned by tape casting in both matrices (orientation parameters r = 0.27 and 0.18, respectively), whereas 0.6 μm diameter templates were well aligned in the seeded boehmite sol only (r = 0.29). Improved alignment in boehmite sols is attributed to inorganic gelation, resulting in a strongly pseudo‐plastic rheology that preserves template alignment against the influence of Brownian motion. The in situ formation of fine α‐Al₂O₃ matrix after transformation in the seeded boehmite system results in a higher driving force for TGG and improves texture development. The combination of 3 μm templates with a seeded boehmite matrix results in extremely high texture qualities (texture fraction f = 0.97–0.99, r = 0.17) while maintaining a relatively fine grain size (5–10 μm in diameter and 1.5–3 μm in thickness). Although undoped samples can be fully textured at 1600°C, adding as little as ~0.25 wt% CaO/SiO₂ dopant improves TGG kinetics and yields full texture at 1400°C.     

Fabrication of Textured Silicon Carbide via Seeded Anisotropic Grain Growth

Highly textured silicon carbide was fabricated via anisotropic grain growth. Large, platelike grains were grown from a fine-grained sintered matrix which had been seeded with ≤2% SiC platelets. The seeds were initially incorporated with preferred orientation during the green-state forming process and this resulted in oriented growth of the platelike grains. The development of texture in the samples was evident from microstructure observations and X-ray diffraction analysis.     

Templated Grain Growth in Macroporous Materials

We demonstrate a facile method to produce crystallographically textured, macroporous materials using a combination of modified ice templating and templated grain growth (TGG). The process is demonstrated on alumina and the lead‐free piezoelectric material sodium potassium niobate. The method provides macroporous materials with aligned, lamellar ceramic walls which are made up of crystallographically aligned grains. Each method showed that the ceramic walls present a long‐range order over the entire sample dimensions and have crystallographic texture as a result of the TGG process. We also present a modification of the March–Dollase equation to better characterize the overall texture of materials with textured but slightly misaligned walls. The controlled crystallographic and morphologic orientation at two different length scales demonstrated here can be the basis of multifunctional materials.     

Templated Grain Growth of <001> Textured PMN-28PT Using SrTiO3 Templates

Highly textured PMN-28PT (0.72Pb(Mg_1/3Nb_2/3)O₃–0.28PbTiO₃) ceramics were produced by templated grain growth on <001> oriented platelet-shaped SrTiO₃ template particles with an aspect ratio of 10–15. The templates were aligned in PMN-28PT matrix powder via tape casting and fired in an O₂–PbO atmosphere at 1150°C for up to 15 h. This resulted in textured ceramics with a 40 micrometer grain size and without residual templates. The volume fraction of textured material (  f  ) and the orientation parameter ( r ) were quantified by fitting X-ray diffraction rocking curve data to the March–Dollase equation. Processing conditions were optimized to achieve the best possible values of f and r for the chosen templates and matrix powder. A texture fraction of at least 81 vol% and an orientation parameter of 0.2 were achieved when all random matrix grains were consumed (a perfect textured ceramic would show a texture fraction of 100 vol% and an orientation parameter of 0).     

Templated Grain Growth of Barium Titanate Single Crystals

BaTiO₃ single crystals were grown via templated grain growth (TGG), which is a process in which a single-crystal "template" is placed in contact with a sintered polycrystalline matrix and then heated to migrate the single-crystal boundary into the matrix. Millimeter-sized, stoichiometric single crystals of BaTiO₃ were produced by heating polycrystalline matrix with a relative density of 97% and a Ba/Ti ratio of <1.00, which was bonded to a BaTiO₃ single crystal, at temperatures above the eutectic temperature. Growth rates of 590–790, 180–350, and 42–59 μm/h were observed for {111}-, {100}-, and {110}-oriented single-crystal templates, respectively. Lower-surface-energy facets were formed for {111}- and {100}-oriented templates, whereas {110} crystals maintained a {110} growth front, which indicated that this plane orientation was the lowest-energy surface in this system. SrTiO₃ also was shown to be a suitable substrate for TGG of BaTiO₃.     

Pb(Mg1/3Nb2/3)O3–PbTiO3 Textured Ceramics with High Piezoelectric Response by a Novel Templated Grain Growth Approach

Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ is used as a model system of perovskite solid solutions with very high piezoelectric response at tailored morphotropic phase boundaries to demonstrate the processing of textured ceramics by ceramic‐only technology. A novel homogeneous templated grain growth approach that uses conventional ceramic procedures and a single‐source nanocrystalline powder for the matrix and also for obtaining the templates is described. Two batches of (100) faceted cube‐shaped microcrystals with average sizes of 27 and 10 μm were successfully used as templates, and aligned by tape casting for the processing of <001>‐textured Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ piezoelectric ceramics. Materials with effective piezoelectric coefficients up to 1000 pC/N and ferroelectric properties approaching those of single crystals are obtained.     

Low‐Temperature Control of Twins and Abnormal Grain Growth in BaTiO3

The microstructure of polycrystalline barium titanate (BaTiO₃) thin films processed with a liquid‐phase can be controlled by the crystallographic orientation of the underlying sapphire substrate. During postdeposition crystallization, the tendency for {111} twin nucleation, which drives subsequent abnormal grain growth, depends upon the specific sapphire facet. Specifically, tilting away from the close‐packed c‐plane modifies the orientation, morphology, and relative amount of an interfacial BaAl₂O₄ second phase. These factors control the density of twin formation, and thus overall grain size of the crystallized BaTiO₃. As the substrate orientation transitions from c‐plane, to r‐plane, to a‐plane, the twin density is reduced, the average grain size decreases systematically from 270 to 130 nm, and the grain structure becomes overall more homogeneous. This twinning mechanism and abnormal grain growth occur by 900°C, several hundred degrees lower than reported previously.     

机械激活前驱体法制备具有异向生长特征的BaTiO3膜

采用高能球磨法对合成BaTiO3的原料混合体系进行高球料比的机械激活处理,经高温固相反应在氧化铝基片上制备了BaTiO3膜.利用X射线(XRD)和扫描电镜(SEM)等手段对试样的成分、结构及表面形貌进行表征分析,研究结果表明利用高能球磨法,以八水氢氧化钡和二氧化钛为主要原料,在球料质量比为30∶1,球磨介质为氧化锆球和尼龙罐,球磨时间为20h的参数条件下激活的粉体经1350℃下高温烧结3h合成的BaTiO3膜成分单一,且具有明显的异向生长特征.     

Normal and Abnormal Grain Growths in BaTiO3 Fibers

The grain growth mechanisms along the BaTiO₃ fibers were studied between 1150°C and 1250°C. The normal grain growth always reached a stagnant stage after certain heat‐treatment duration caused by the surface pinning effect. However, the abnormal grain growth (AGG) was not pinned by such surface effect, and can grow continuously. The confined normal grain (or matrix grain) size provides the driving force for AGG. The fiber diameter has an important influence on the grain growth behaviors. Submicrometer fibers have relative small stagnant grain sizes, resulting in large driving force for AGG. Abnormal grain growth occurred below 1200°C in the submicrometer diameter fibers, but was not observed at the same temperature in the fibers with diameter of above 1 μm. Due to the large AGG driving force, large number densities of abnormal grains were observed in submicrometer fibers, resulting in “bamboo‐like” microstructure. Fibers with diameters of 1–2 μm were able to be converted into single crystal fibers up to several tens of micrometers due to the relative small AGG driving forces.     

Texture Development by Templated Grain Growth in Liquid-Phase-Sintered α-Alumina

The distribution and orientation of platelet-shaped particles of α-alumina in a fine-grained alumina matrix is shown to template texture development via anisotropic grain growth. The textured microstructure ranges from 4 wt% oriented platelet particles in calcined samples to nearly 100% oriented α-Al₂O₃ grains after sintering at 1400°C. A CaO + SiO₂ liquid phase creates favorable thermodynamic and kinetic conditions for anisotropic grain growth and grain reorientation during sintering. Important criteria for templated grain growth include (1) anisotropic crystal structure and growth, (2) high thermodynamic driving force for template grain growth, and (3) modification of diffusion in the system to continuously provide material to the anisotropically growing template grains.     

Crystallographic Orientation Analysis on Calcium Cobaltite Ceramic Grains Textured by Reactive-Templated Grain Growth

Textured thermoelectric [Ca₂CoO₃]_0.62[CoO₂] (denoted as CCO) ceramic was fabricated and distributions of crystallographic orientations for local grains and misorientation angles between grains were investigated by electron backscatter diffraction pattern analysis. Most of the grains are preferentially aligned with their conductive ab -planes parallel to the original tape-casting surface. Parallel aligned boundaries are observed in a single grain and the nearest neighboring crystallites sharing these boundaries have misorientation angles of multiples of 60°. It is suggested that these unique domain structures are formed during the topotactic nucleation and growth of monoclinic CCO phase on its precursor Ca _x CoO₂ in a hexagonal crystal system.     

Computational Design for Grain-Oriented Microstructure of Functional Ceramics Prepared by Templated Grain Growth

We have developed a computational model using Monte Carlo simulation in order to design grain-oriented microstructures of ceramics processed by templated grain growth for functional materials with anisotropic grain growth due to anisotropy in interfacial energies. The current model with plate-like template particles expressed the development of grain-oriented microstructures with the low interfacial energy planes well faceted. In addition, the proposed model gave a guiding principle for optimizing the initial parameters (i.e., ratio of templates to total solid particles, initial size and aspect ratio of template particles, and amount of liquid phase), leading to highly grain-oriented ceramics with improved performances.     

Electrically Active and Inactive Single Grain Boundaries in Semiconducting BaTiO3

Bi‐crystal specimens were prepared from Nb and Mn‐doped BaTiO₃ poly‐crystals with giant grains of millimeter order in size, and the resistance (R) versus temperature (T) characteristics of these individual grain boundaries was investigated. The electrically active grain boundaries that show normal positive temperature coefficient resistor (PTCR) behavior had no second phases or they were partially distributed along boundaries. On the other hand, electrically inactive grain boundaries that show flat R‐T characteristics were also observed, where continuous Ti‐rich second phases of Ba₄Ti₁₂O₂₇ could be detected. Different interface state density and its resultant R–T characteristics were observed for each individual active boundary, which indicates the degree of oxidation and the formation of potential barrier can be different depending on the character of the grain‐boundary plane. The resistance of inactive boundaries was determined by that of insulating second phase showing negative temperature coefficient resistor (NTCR) behavior. These results demonstrate that continuous second phase surrounding a grain deactivates the electrical properties of grain boundary, and thus should be distinguished from insulating depletion layer near grain boundary.     

Rapid Formation of Nanocrystalline BaTiO3 and Its Highly Stable Sol

Ultrafine BaTiO₃ nanoparticles and their highly stable sols are prepared by a novel and rapid route. In this method, the formation mechanism that lies between the chemical precipitation and the sol–gel process is proposed. The BaTiO₃ nanocrystal sols are synthesized in as fast as 15 min in an air atmosphere. Dynamic light scattering analysis and the observation of the Tyndall effect confirm the existence of crystalline nanoparticles in these sols. After careful separation, nanocrystalline BaTiO₃ powders with an average particle size as small as 2.8 nm are obtained. These particles have perovskite phase structures as determined by X‐ray diffraction and selected‐area electron‐diffraction analysis. Fourier transform infrared spectroscopy (FT‐IR) and thermal analysis are used to detect the characteristic functional groups of the solvents on the particles to reveal the formation mechanism. Uniform BaTiO₃ nanocrystal films with high dielectric constants, low dielectric losses, and paraelectric behavior are prepared through solvent evaporation of the nanocrystal sols, providing a new low‐temperature route for the fabrication of perovskite thin films.     

Grain size effect on piezoelectric and ferroelectric properties of BaTiO3 ceramics

A series of dense barium titanate (BaTiO₃, BTO) ceramics with different grain sizes (GS) were prepared by two-step sintering method. The effect of GS on piezoelectric coefficient (d₃₃) and planar electromechanical coupling factor (k_p) displayed a trend similar to that on relative permittivity (ɛ′). The values of d₃₃, k_p, and ɛ′ increased significantly with decreasing GS, reaching maximum values (ɛ′ = 6079, d₃₃ = 519 pC/N and k_p = 39.5%) at approximately 1 μm, and then decreased rapidly with further decreasing GS. The results revealed that high-performance BTO ceramics could be effectively prepared by controlling GS. Polarization–electric field hysteresis loops and temperature dependence of ɛ′ were also investigated.     

Origin of Texture Development in Barium Bismuth Titanate Prepared by the Templated Grain Growth Method

Microstructure development was examined for BaBi₄Ti₄O₁₅ prepared by the templated grain growth method, and the origin of texture development was discussed. The microstructure development in a compact composed of a platelike template and equiaxed matrix grains was characterized as follows: (1) the template grains thickened at an early stage; (2) the matrix grains changed their shape from equiaxed to platelike, and simultaneously, the plate faces aligned parallel to those of template grains; and (3) a group of large grains with mutually parallel alignment was formed by prolonged heating at high temperature. Texture developed during these microstructural changes, and process (2) made the greatest contribution toward texture development.