Microstructure and Grain Boundary Structure of Na+-Diffused (Sr,Ca)TiO3 Capacitor-Varistor Ceramics

The microstructure of (Sr,Ca)TiO₃ capacitor-varistor materials has been investigated by employing electron microscopy techniques (TEM, STEM, HREM, EDX, and EPA). The material is found to contain (Sr,Ca)TiO₃ grains (∼30 μm) having perovskite crystal structure with domains, a Na⁺-diffused layer at the grain boundaries which is dependent on thermal diffusion conditions, and multiple-grain junctions in which the Ti _n O_2n–1 Magneli phase coexists with an amorphous intergranular phase. In addition, wider grain boundaries (10–30 nm), thin grain boundaries (∼1 nm), and clean grain boundaries which are free from intergranular phase were observed, and the effects of different grain boundaries on the diffusion of Na⁺are discussed.     

Microstructure observation of β-sialon-15R ceramics synthesized from aluminum dross

Fully dense β-sialon-15R multiphase ceramics were synthesized by hot pressing sintering using aluminum dross as raw material. Transmission electron microscopy (TEM) was used to study the microstructure, notably for the impurity and glass phase. The results show that β-sialon grains are generally equiaxed, and 15R AlN polytypoid grains show a fibre-like morphology. The main impurity phase is Fe₅Si₃. High resolution electron microscopy (HREM) results confirm the interface between β-sialon grains and/or 15R grains to be clean in the sample synthesized at 1750 °C, and the glassy phase only exist in triple junctions and pockets. AlN polytypoids in the multiphase ceramics provide a path to reduce the glass phase formed from the oxide impurity in aluminum dross.     

Microstructure, Microchemistry, and Flexural Strength of Mullite Ceramics

The microstructure of mullite ceramics hot-pressed and sintered at different temperatures was studied using transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM) with EDS, and electron probe microanalysis (EPMA). The specimens, consisting of stoichiometric mullite grains without glassy phase, are obtained by hot-pressing stoichiometric mullite powder at 1575°C for 1 h. Silica-rich glassy phases are observed using TEM at three-grain junctions of mullite grains in specimens heated at and above 1600°C. However, high-resolution transmission electron micrographs show no glassy phase at two-grain boundaries in all specimens. SEM with EDS analyses show that the average value of Al₂O₃ contents of mullite grains increases slightly with increasing temperature. These results are consistent with a published Al₂O₃–SiO₂ phase diagram. The flexural strength of mullite specimens at room temperature depends on their microstructure, such as the grain size and grain size distribution of mullite grains. The strength is high at room temperature and up to 1200°C, and it decreases at and above 1350°C, irrespective of the presence of the glassy phase.     

Phase Analysis and Thermal Stability of Hot Isostatically Pressed Zirconia–Hydroxyapatite Composites

Composites of zirconia and hydroxyapatite (OHAp) have been processed via hot isostatic pressing (HIP) or sintering in air. When the composites were sintered in air at a temperature of 950°C, decomposition of the OHAp to tricalcium phosphate occurred. Using the HIP technique, composites without any detectable degradation of the OHAp phase were produced at 1200°C. The reactivity between zirconia and OHAp was dependent on both the amount of water lost from OHAp and the geometry of the interaction. The phase composition of the materials prepared was evaluated from their powder X-ray diffraction patterns, and their microstructures were studied via electron microscopy.     

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Characterization of Glass Phase in Sol-Gel-Derived Mullite

Sol-gel-derived mullite ceramics were processed by pressureless sintering at 1600°, 1650°, and 1700°C for 4 h. Microstructural and microchemical characterization of the mullite materials was performed using transmission electron microscopy, in conjunction with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy (EELS). Apart from mullite grain diameter and triplepocket size, no major microstructural changes were observed with increasing sintering temperature. Residual glass was present at triple pockets and along two-grain junctions. Not all grain boundaries revealed the presence of a continuous amorphous intergranular film. Clean interfaces were observed only at boundaries with one grain parallel to the [001] orientation (low-energy configuration). Quantitative EELS analysis of mullite grains and glass pockets revealed only small changes in composition with increasing sintering temperature; i.e., the alumina:silica ratio slightly increased for mullite and glass. The analysis implied that mullite with this relatively high aluminum content would not be stable adjacent to residual glass. However, a stable glass-mullite system has been proposed, because impurity cations were detected within glass pockets, which suggested a slight shift of the subsolidus line (glass-mullite/ mullite) to a higher amount of alumina. Energy-loss nearedge structure studies of the Si- L _2,3 edge revealed a similar near-edge structure for the mullite, residual glass, and quartz. Thus, SiO₄ tetrahedra were thought to be the main building units of the glass contained in sintered mullite.     

Influence of SiO2 and CaO additions on the microstructure and magnetic properties of sintered Sr-hexaferrite

The effect of simultaneous addition of CaO and SiO₂ on the microstructure and magnetic properties of sintered SrO-excess Sr-hexaferrites was studied. Both additives markedly affect the grain growth behavior and the magnetic properties. CaO-additions promote densification, which results in increased remanence, but due to simultaneuous grain growth the coercivity drops to <100 kA/m. SiO₂ additions are known to suppress grain growth. Simultaneous addition of CaO and SiO₂ is shown to be very beneficial in tailoring a dense microstructure with relatively small grains. The ratio of CaO/SiO₂ was found to be optimum at about 1, and magnets with a remanence of 430 mT and a coercivity of 300 kA/m were obtained. Transmission electron microscopy (TEM) studies and investigations by energy-dispersive analysis of X-rays (EDX) in the scanning TEM (STEM) mode show that both CaO and SiO₂ are concentrated at grain boundaries and grain junctions forming an amorphous secondary phase.     

晶界相对半透明氮化铝陶瓷透过率的影响

分别添加质量分数为3%的CaF2和Y2O3为烧结助剂,在相同烧结工艺制度下采用放电等离子烧结(spark plasma sintering,SPS),制备了两种半透明AlN陶瓷.两种样品有相近的密实度和晶粒尺寸,但是它们的透过率却相差很大.用扫描电镜,X射线衍射分析和透射电镜结合能量散射型X射线光谱分析仪对样品微观结构进行分析.结果表明:晶界相的存在及分布方式对样品透过率有重要影响.添加CaF2的样品表现出很高的纯度,晶界及三角晶界处观察不到第二相.添加Y2O3的样品中,由于生成的晶界相Y3Al5O12沿AlN晶界分布,阻隔AlN晶粒之间的连接,在晶界处造成光散射,导致样品透过率下降.     

Diffraction Method Detection of Local Lattice Distortion in AIN Ceramics by Convergent Beam Electron

Lattice distortions in polycrystalline aluminum nitride (A1N) were observed by convergent beam electron diffraction (CBED). CBED patterns show that the A1N crystal lattice is distorted near the grain-boundary phase. This is a result of sintering aids, possibly due to the difference in the thermal expansion between the AlN crystal and the grain-boundary phase.     

Cubic-Formation and Grain-Growth Mechanisms in Tetragonal Zirconia Polycrystal

The microstructure in Y₂O₃-stabilized tetragonal zirconia polycrystal (Y-TZP) sintered at 1300°–1500°C was examined to clarify the role of Y³⁺ ions on grain growth and the formation of cubic phase. The grain size and the fraction of the cubic phase in Y-TZP increased as the sintering temperature increased. Both the fraction of the tetragonal phase and the Y₂O₃ concentration within the tetragonal phase decreased with increasing fraction of the cubic phase. Scanning transmission electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDS) measurements revealed that cubic phase regions in grain interiors in Y-TZP generated as the sintering temperature increased. High-resolution electron microscopy and nanoprobe EDS measurements revealed that no amorphous layer or second phase existed along the grain-boundary faces in Y-TZP and Y³⁺ ions segregated at their grain boundaries over a width of ∼10 nm. Taking into account these results, it was clarified that cubic phase regions in grain interiors started to form from grain boundaries and the triple junctions in which Y³⁺ ions segregated. The cubic-formation and grain-growth mechanisms in Y-TZP can be explained using the grain boundary segregation-induced phase transformation model and the solute drag effect of Y³⁺ ions segregating along the grain boundary, respectively.     

Highly dense and fine-grained SiC with a Sc-nitrate sintering additive

To explain the sintering behavior of 5 wt.% Sc-nitrate-added SiC, which showed a 99.3% density with the fine 156 nm-sized grains, a microstructural study using high resolution electron microscopy (HREM) was performed and the results were compared with those of Tm-added SiC, which had a mean grain size of 753 nm. Contact flattening was proposed as a governing sintering mechanism for Sc-added SiC based on the experimental observations of an inter-granular phase thinner than 1 nm along with the straight grain boundaries. On the other hand, the Tm-added SiC showed a several nm-thick inter-granular phase with a curved grain boundary morphology, which is the typical microstructure that can be obtained by a solution–reprecipitation mechanism combined with Ostwald ripening.     

Electron microscopy of shock deformation in alumina

Shock recovered samples of a coarse grain (10 μm), high density (>99.9% theoretical) alumina from asymmetric impact tests conducted at 6.5 GPa (e.g. 3.2 times its Hugoniot Elastic Limit) in a single stage gas gun and characterized by X-ray diffractometry, scanning and field emission scanning electron microscopy, and transmission electron microscopy showed prolific presence of reduced crystallite size, higher average microstrain, grain localized micro/nano-scale deformations, micro-cleavages, grain-boundary microcracks, micro-wing crack formation, extensive shear induced deformations and fractures localized at grains, grain boundaries and triple grain junctions, grain localized entanglement of dislocations and their pile up impeded at grain boundaries. A new qualitative model based on micro-shear and micro-twist induced deformation and fracture in single and/or multiple planes in suitably oriented grain and/or grain assembly was developed to explain the experimentally observed damage evolution process.     

Electron microscopy study of the microstructure of a hot-pressed silicon nitride

A microstructural investigation of a commercial hot-pressed silicon nitride variety is reported here; electron microscopy observations have been performed in attempt to precisely] characterize the microstructure of the material. In particular, grain boundary structures have been studied by transmission electron microscopy using bright and dark-field techniques; a typical amorphous phase has been revealed in triple junctions and along grain boundaries.     

Nanostructural insights into the dissolution behavior of Sr-doped hydroxyapatite

In this study, high-resolution transmission electron microscopy (HRTEM) was employed to characterize the nanostructure of strontium-substituted hydroxyapatite (Sr-HA) and its evolution following in vitro immersion in physiological solutions. HRTEM images showed that the substitution of Sr induced local distortions in the hydroxyapatite (HA) lattice: minor levels of edge dislocations were detected at low doping contents of Sr ions (1 at%); when the Sr content exceeded 10 at%, the density of grain boundaries increased notably and triple junctions were clearly observed. The dissolution of undoped HA was initiated at crystallite surfaces, whereas the dissolution of Sr-HA started around grain boundaries. Acicular nanocrystal reprecipitation was observed on grain surfaces immersed in simulated body fluid (SBF), while not in dilute hydrochloric acid (HCl). These ?ndings suggest appropriate levels of Sr incorporation can introduce imperfections in the crystal structure of apatite and thus enhance its dissolution rate towards enhanced physicochemical performance in biomedical applications.     

A Novel Processing Route to Control Grain Growth in Submicrometer Alumina Compacts

A novel processing procedure for significantly suppressing grain growth in submicrometer alumina compacts has been developed and implemented with the intent of ultimately using the same processing route to control grain size in nanophase alumina compacts. In this study, partially sintered alumina pellets made from 0.5 µm starting powders are altered by the chemical infiltration of Si₃N₄. The control and infiltrated pellets are then heated to 1650°C for 4 h. The fully sintered pellets are approximately 97% dense. Suppressed grain growth is observed in the infiltrated pellets. The average grain size in the control pellets after densification is 4.2 and 1.2 µm in the infiltrated pellets. Depth of infiltration is measured using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Depending on the specific infiltration conditions used, the outer 15-50% of the infiltrated pellets exhibit a graded microstructure consisting of a region of abnormal grain growth and a region of suppressed grain growth. Abnormal grain growth is visible on the outer surfaces of the infiltrated pellets where a relatively high ratio of Si to N is present. Further into the pellet, after some depletion of the Si source gas has occurred, regions of suppressed grain growth are apparent. Based on these results, an infiltration profile is determined. A mathematical model is developed to describe the infiltration process and to determine optimal infiltration conditions. High-resolution electron microscopy (HREM), energy dispersive spectroscopy (EDS), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS) are used to study the infiltrated samples.     

Influence of SiAlON addition on the microstructure development of hot-pressed ZrB2–SiC composites

The impact of SiAlON on densification behavior and microstructure of the ZrB₂-SiC composite was investigated. ZrB₂, SiC, and SiAlON were used as the initial materials to produce ZrB₂-SiC composite by hot pressing at 1900 °C. A fully dense composite was obtained having ~99.9% relative density. High-resolution X-ray diffraction (HRXRD) assessment verified the in-situ formation of ZrC, and the presence of residual carbon, SiAlON, and ZrB₂ and SiC phases in the as-sintered ceramic. Furthermore, the thermodynamic calculations confirmed the results attained by HRXRD. In addition, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were utilized for the microstructural investigation. SEM fractographs indicated the impact of SiAlON on the hindering of grain growth and the formation of flaky phases (graphitized carbon or solidified liquid phase) at the grain boundaries. TEM studies revealed the presence of a transparent glassy phase at the particle interfaces. A significant impact of liquid phase sintering was also affirmed in the clean interfaces.     

Diffusion-Induced Grain-Boundary Migration in Ceria-Stabilized Tetragonal Zirconia Polycrystals

The microstructure and microchemistry of grain-boundary regions in (CeO₂+ La₂O₃)-stabilized tetragonal ZrO₂ polycrystals (Ce(La)-TZP) were studied by means of transmission electron microscopy (TEM). Evidence was found for the existence of crystalline and vitreous intergranular phases situated in small pockets at multiple grain junctions and in thin films along grain boundaries. In this ceramic system grain-boundary migration was observed in situ in the TEM in sample areas subjected to electron irradiation. Interfaces migrated away from their centers of curvature. Evidence was found for Ce de-alloying in the volume swept by the advancing boundaries. It is suggested that the coherency lattice strain brought about by a partial reduction of Ce, resulting in the diffusion of Ce³⁺ along grain boundaries to free surfaces, is the driving force for this phenomenon.     

Grain-Boundary Wetting-Dewetting in z= 1 SiAlON Ceramic

The grain-boundary structure of a model SiAlON polycrystal with nominal composition Si₅AlON₇ was characterized by transmission electron microscopy (TEM) both in an equilibrium (as-processed) state at room temperature and after quenching from elevated temperature. In addition, low-frequency (1–13 Hz) internal friction data were recorded as a function of temperature, showing a pronounced grain-boundary sliding peak positioned at 1030°C. High-resolution transmission electron microscopy (HRTEM) of the equilibrated low-temperature microstructure revealed residual glass only at multigrain junctions, but no amorphous intergranular films were observed. The detection of clean interfaces in the as-processed sample contradicts the internal friction data, which instead suggests the presence of a low-viscosity grain boundary phase, sliding at elevated temperatures. Therefore, a thin section of the as-sintered material was heated to 1380°C and rapidly quenched. HRTEM analysis of this sample showed, apart from residual glass pockets, wetted grain boundaries, which is in line with the internal friction experiment. This wetting-dewetting phenomenon observed in z = 1 SiAlON is expected to have a strong impact not only on high-temperature engineering ceramics but also on geological, temperature-activated processes such as volcanic eruptions.     

B6O: A Correlation Between Mechanical Properties and Microstructure Evolution upon Al2O3 Addition During Hot Pressing

B₆O powders were hot pressed with and without Al₂O₃ as a sintering additive at temperatures up to 1900°C and a pressure of 50 MPa. The microstructure of a doped and undoped sample was studied by transmission electron microscopy techniques. This paper aims at studying the correlation between micro/nanostructure evolution and the resulting mechanical properties; i.e., hardness and fracture toughness. The addition of alumina yields the formation of a secondary aluminum borate phase in addition to promoting grain growth strongly. While the addition of Al₂O₃ slightly decreased the hardness of the B₆O polycrystals, the corresponding fracture toughness was strongly improved, as compared with the undoped material.     

Microstructure of (Hf-Ta-Zr-Nb)C high-entropy carbide at micro and nano/atomic level

A High Entropy (Hf-Ta-Zr-Nb)C Ultra-High Temperature Ceramic (UHTC) was fabricated by ball milling and Spark Plasma Sintering (SPS) with a density of 99%. The microstructure characteristics were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) in combination with electron back scattered diffraction (EBSD) and transmission electron microscopy (TEM). Atomic structure and local chemical disorder was determined by means of scanning transmission electron microscopy (STEM) in conjunction with energy dispersive X-ray spectroscopy (EDS). According to the results, high purity, dense and homogeneous high entropy carbide with Fm-3?m crystal structure was successfully produced. The grain size ranged from approximately 5?μm to 25?μm with average grain size of 12?μm. Chemical analyses proved that all grains had the same chemical composition at the micro as well as on the nano/atomic level without any detectable segregation. The approximately 1.5?nm thin amorphous grain boundary phase contained impurities that came from the starting powders and the ball milling process.     

Microstructural Analysis of Liquid-Phase-Sintered β-Silicon Carbide

The microstructures of fine-grained β-SiC materials with α-SiC seeds annealed either with or without uniaxial pressure at 1900°C for 4 h in an argon atmosphere were investigated using analytical electron microscopy and high-resolution electron microscopy (HREM). An applied annealing pressure can greatly retard phase transformation and grain growth. The material annealed with pressure consisted of fine grains with β-SiC as a major phase. In contrast, the microstructure in the material annealed without pressure consisted of elongated grains with half α-SiC. Energy-dispersive X-ray analysis showed no differences in the amount of segregation of aluminum and oxygen atoms at grain boundaries, but did show a significant difference in the segregation of yttrium atoms at grain boundaries along SiC grains for the two materials. The increased segregation of yttrium ions at grain boundaries caused by the applied pressure might be the reason for the retarded phase transformation and grain growth. HREM showed a thin secondary phase of 1 nm at the grain boundary interface for both materials. The development of a composite grain consisting of a mixture of β/α polytypes during annealing was a feature common to both materials. The possible mechanisms for grain growth and phase transformation are discussed.