Microstructure and Crystal Phases of Praseodymium Oxides in Zinc Oxide Varistor Ceramics

The effect of sintering temperature on the microstructure and crystal phases of the intergranular praseodymium oxides in ZnO varistor ceramics was investigated using transmission electron microscopy and high-resolution electron microscopy. The ZnO grains were three-dimensionally separated from the intergranular praseodymium oxides. On the basis of microdiffraction analyses of the intergranular layer, the phase transformation from fcc-Pr₆O₁₁ into hcp-Pr₂O₃ was found when the sintering temperature increased from 1300° to 1350°C. The defect reaction equation and the decrease of donor concentration with increasing sintering temperature can verify the certainty of phase transition during the liquid-phase sintering observed by transmission elecron microscopy. Additionally, on the basis of the small variations of the breakdown voltage per grain boundary, the number of active grain boundaries is not a dominant factor for the donor concentration dependence on the sintering temperature.     

Alumina based ceramics for high-voltage insulation

Dielectric breakdown constitutes an important limitation in the use of insulating materials under high-voltage since it can lead to the local fusion and sublimation of the insulator. The role of electrical charge transport and trapping in alumina ceramics on their resistance to this catastrophic phenomenon is studied in this work. In polycrystalline materials, the interfaces between the various phases play a main role because they constitute potential sites for the trapping of electrical charges. The density and the nature of these interfaces can be controlled by the way of the microstructure parameters. So, the aim of the present paper is to highlight the influence of average grain size and intergranular phase crystallization rate on the ability of polycrystalline alumina materials to resist to dielectric breakdown. Thus, it is shown that the control of the process conditions (sintering aids content, powder grain size and thermal cycle) makes it possible to change not only the density (by the average grain size) but also the nature (by the crystallization or not of anorthite) of the grain boundaries. On one hand, at room temperature a high density of interfaces, due to low grain size and highly crystallized intergranular phase, leads to a high dielectric strength. On the other hand, at higher temperature (250 °C), the presence of vitreous intergranular phase makes it possible to delay breakdown. That behaviour is explained thanks to charge transport and trapping characterizations.     

Normal sintering of (K, Na)NbO3-based lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics have received more attention due to the environmental protection of the earth. (K, Na)NbO₃-based ceramics are one of the most promising candidates. Normal sintering of un-doped and Li/Ta co-doped (K, Na)NbO₃ ceramics was investigated to clarify the optimal sintering condition for densification, microstructure and electrical properties. It was found that density increased greatly within a narrow temperature range but turned to decrease when the sintering temperature slightly exceeded the optimal one. Piezoelectric properties also showed similar relationship between the density and sintering temperature, but the highest piezoelectric strain coefficients were obtained at the temperatures lower than that for the highest density. The grain growth and property change as a function of sintering temperature were discussed on basis of the formation of liquid-phase and the composition deviation caused by the volatilization of alkali components during sintering.     

Graphitic Materials Hot-Worked with a Dispersed Liquid Carbide: Thermal and Electrical Conductivity

Graphitic materials produced by hot-working with a dispersed liquid-carbide phase (termed HWLC graphites) have high thermal and electrical conductivities compared with hot-worked or conventional graphites prepared without additives. Thermal diffusivity and electrical conductivity were measured at room temperature on two HWLC materials containing either molybdenum carbide or zirconium carbide. This process of liquid-phase sintering with compressive deformation imposes a strong preferred orientation on the predominantly graphitic material, and the resulting thermal conductivity in the preferred direction of the layer planes is greater than the thermal conductivity of copper or silver. Thus, liquid-phase stress sintering induces in graphitic materials an essentially new microstructure that provides a means of realizing the inherent high thermal conductivity of the graphite layer plane in a massive body.     

Control of multiphase evolution and Al-deficiency in reactive-sintered MoAlB ceramics with excessive Al

MoAlB is a ternary boride of MAB phases with strong resistance to oxidation and ablation at service temperature, thanks to preferential Al diffusion to form a protective oxide scale. However, excessive Al were often necessary in sintering of MoAlB ceramics, suggesting that a liquid-phase densification might occur thus leading to complex microstructures. By quantitative SEM analysis, ~17 mol.% Al₂O₃ phase was found common in MoAlB ceramics. The liquid-phase of Al-Mo-B-O facilitates the direct conversion from MoB to MoAlB before in situ formation of Al₂O₃. An intermediate Mo₃Al₈ phase competes with layered conversion, which limits the insertion rate of Al into B-B layers of MoB to form abundant Al-deficient stacking-faults. Intermetallic Mo₃Al₈ phase precipitates further in the intergranular regions parallel to the crystallization of Al₂O₃, leaving the reprecipitation of remaining Al. Both layered-conversion and intergranular oxides can improve ablation behavior for MoAlB ceramics, as well as fracture toughness and compressive strength.     

Microstructures and mechanical properties of functionally graded TiCN–TaC ceramics prepared by a novel layer processing strategy

Functionally graded TiCN–TaC ceramics (FGTTCs) were fabricated using a novel layer processing method based on a vacuum hot-press sintering technology. Microstructural investigations revealed a visibly layered structure for the FGTTCs with relatively flat boundaries between the neighboring layers; additionally, the layer thickness was facilely controlled. With an increase in the sintering temperature, the hardness and flexural strength of the surface and middle layers of the FGTTCs initially increased, and then decreased. The fracture toughness of the surface layer did not undergo significant changes after sintering at various temperatures, except at 1500 °C. The FGTTC sintered at 1350 °C contained uniform fine grains and simultaneously exhibited transgranular and intergranular fracture modes. Further, it presented excellent comprehensive mechanical properties, i.e., surface layer hardness = 20.28 ± 0.18 GPa, flexural strength = 1553.76 ± 22 MPa, surface layer fracture toughness = 7.29 ± 0.24 MPa m^1/2. Under the same sintering conditions, our FGTTCs presented superior mechanical properties against homogeneous TiCN–TaC ceramics (HTTCs), achieving a considerably higher flexural strength (1553.76 ± 22 vs 953.35 ± 24 MPa).     

Composition,microstructure and electrical properties of K0.5Na0.5NbO3 ceramics fabricated by cold sintering assisted sintering

In this paper, cold sintering was served as a forming method to assist the conventional sintering, which is so-called cold sintering assisted sintering (CSAS) method. Lead-free K_0.5Na_0.5NbO₃ piezoelectric ceramics were prepared by the CSAS method, and the effects of the different procedures on the sintering behaviors and electrical properties of KNN ceramics were studied. Compared with conventional sintering (CS), cold sintering process can induce potassium-rich phase on the KNN particle surface, and remarkably increase both the green and sintering density of KNN ceramics. Meanwhile, the potassium-rich phase would transform to K₄Nb₆O₁₇ second phase on the grain surface, and subsequently suppress the volatilization of potassium element. The sinterability and electrical properties were greatly improved, and KNN piezoelectric ceramics with high performance can be manufactured in a wide sintering temperature range (1055 °C–1145 °C), which proves that CSAS has the potential to be an excellent sintering technique for producing KNN based ceramics.     

Transmission Electron Microscopy at Grain Boundaries of PTC-Type BaTiO3 Ceramics

Transmission electron microscopy of the grain boundaries of Ti-rich semiconducting PTC-type BaTiO₃ ceramics is described. At a width of 2 to 10 nm, there were no indications of intergranular second-phase layers covering the grains. Second phase was segregated only at the contacts of three or more grains; electron diffraction confirmed the amorphous structure of this phase. Observed ferroelectric domains at the grain boundaries do not indicate a PTC-specific orientation of ferroelectric domains due to the negative grain surface charge.     

Sintering Behavior and Surface Microstructure of PbO-Rich PbNi1/3Nb2/3O3–PbTiO3–PbZrO3 Ceramics

The sintering behavior and surface microstructure of PbNi_1/3Nb_2/3O₃–PbTiO₃–PbZrO₃ (PNiNb-PT-PZ) ceramics were investigated. The PNiNb-PT-PZ ceramics with the stoichiometric composition and the addition of excess lead oxide (PbO-rich ceramics) were sintered by liquid-phase sintering in accordance with the solution-reprecipitation mechanism at temperatures below the melting point of PbO. The temperature at which the liquid phase forms fell to near the eutectic point of the PbO–Nb₂O₅ and the PbO–TiO₂ system (868°C) with the addition of 5 mol% PbO. As the calcination temperature influenced the sinterability of the stoichiometric PNiNb-PT-PZ ceramic, unreacted PbO was considered to be the source of the liquid phase in the sintering of the stoichiometric powder. The secondary phase was observed at the surface of PbO-rich ceramics and was suggested to be a liquid phase expelled from inside the ceramic. A sintering scheme of PNiNb-PT-PZ ceramics was proposed, and the high sinterability of PNiNb-PT-PZ ceramics was attributed to the low formation temperature of the liquid phase.     

Elektrische Doppelschichten: Elektrostatik und Elektrodynamik

Electrical Double Layers: Electrostatics and Electrodynamics Dispersions of solid particles in aqueous solutions almost invariably bear a surface charge which is compensated by an opposite charge in the solution. An electrical double layer is formed. The surface charge can sometimes be determined by titration. In practice, the electrokinetic potential or zeta potential is usually measured. This potential is a characteristic quantity for stability, rheology, sedimentation, etc., of disperse systems. This paper addresses the question of the relation of the electrokinetic potential to the static double layer parameters. To this end the author provides a detailed account of electrokinetic shear processes. In addition, new results obtained with the aid of molecular dynamics are also presented.     

Phase Transformations and Melting Effects During the Sintering of Bismuth-Doped Zinc Oxide Powders

ZnO ceramics used as varistors are prepared with bismuth oxide as an essential additive. Some of its effects during the first step of liquid-phase sintering remain unexplained. Therefore, in this work, we characterize the Bi distribution and identify the Bi-rich phases in spherical Bi-chemically-doped ZnO powders. By a suitable method of differential thermal analysis conducted during sintering, we detect thermal phenomena. Characterization of ceramics quenched during sintering allows us to describe them and to analyze their influence on sintering. We also study the parameters which determine the occurrence of these events during sintering.     

Electrically conductive SiC ceramics processed by pressureless sintering

Polycrystalline SiC ceramics with 10 vol% Y₂O₃-AlN additives were sintered without any applied pressure at temperatures of 1900-2050°C in nitrogen. The electrical resistivity of the resulting SiC ceramics decreased from 6.5 × 10¹ to 1.9 × 10⁻² Ω·cm as the sintering temperature increased from 1900 to 2050°C. The average grain size increased from 0.68 to 2.34 μm with increase in sintering temperature. A decrease in the electrical resistivity with increasing sintering temperature was attributed to the grain-growth-induced N-doping in the SiC grains, which is supported by the enhanced carrier density. The electrical conductivity of the SiC ceramic sintered at 2050°C was ~53 Ω⁻¹·cm⁻¹ at room temperature. This ceramic achieved the highest electrical conductivity among pressureless liquid-phase sintered SiC ceramics.     

ⅡA族钙钛矿型氧化物半导瓷的结构与特性

研究了用于表面层和晶粒边界层型的BaTiO3,SrTiO3陶瓷的还原、再氧化、掺杂与替位固溶的情况,并对这类陶瓷的半导体特性与工艺过程的关系作了讨论,文中指出：只有良好的再氧化层才能具有良好的介电特性,而不是颗粒间的二相物质。     

烧结工艺对石英质多孔陶瓷性能的影响

以石英砂为主要原料,采用液相烧结法,经半干压成型制备石英质多孔陶瓷.采用SEM对多孔陶瓷的显微结构进行表征.探讨了烧结温度、保温时间对多孔陶瓷孔隙率及断裂强度的影响.结果表明:随着烧结温度升高,保温时间延长,石英质多孔陶瓷的孔隙率下降、断裂强度不断增大;最佳烧结温度为1250℃,最佳保温时间为30 min.在最佳烧结工艺条件下,制备得到高孔隙率陶瓷,孔结构单一且孔径分布较窄,平均孔径大约为12.41μm.     

Preparation, Structure, and Properties of Thermally and Mechanically Improved Aluminum Titanate Ceramics Doped with Alkali Feldspar

Aluminum titanate (AT) ceramic materials doped with alkali feldspar ((Na_0.6K_0.4)AlSi₃O₈) have been prepared. These ceramics exhibited high sinterability, large resistance to thermal decomposition, and large flexure strength. The existence of liquid-phase feldspar at sintering temperatures promoted the formation of AT ceramics as the sintering agent. It was considered that silicon ions substituting for aluminum ions at the surface of AT crystal grains lowered the surface energy and hindered the diffusion of Ti⁴⁺ and Al³⁺, giving rise to the large resistance to thermal decomposition. As a result, doping with alkali feldspar was found to effectively improve the mechanical and thermal properties of AT ceramics.     

氧化铝陶瓷低温烧结的研究现状和发展前景

本文综述了氧化铝陶瓷低温烧结的研究现状,包括粉体的制备,处理,成型及烧结工艺,并对此领域做了相应的设想和展望。     

Influence of sintering temperature on the crystallization and mechanical properties of BN-MAS composites

A type of boron nitride–magnesium aluminum silicate (BN-MAS) composite ceramics was fabricated by hot-press sintering at different sintering temperatures. The relationship between the sintering temperature and microstructure was investigated by analyzing the interaction between hexagonal boron nitride (h-BN) and the MAS phase. The main MAS phase in the composite ceramics is the α-cordierite phase at a sintering temperature of 1300°C. At temperatures above 1400°C, the inhibitory effect of h-BN on the crystallization of the MAS system is significant, and MAS mainly exists in the form of an amorphous phase. The composite sintered at 1700°C exhibited the highest bending strength of 218MPa. h-BN and MAS were co-enhanced. MAS can be used as an effective liquid-phase sintering aid to assist in the sintering of h-BN, whereas h-BN can absorb the fracture energy of the composite ceramics through the pull-out and bridging effect of the particles.     

Fabrication of dense and defect-free diffusion barrier layer via constrained sintering for solid oxide fuel cells

To enable the development of next-generation solid oxide fuel cells (SOFCs), the fabrication of dense and defect-free diffusion barrier layers via constrained sintering has been a significant challenge. Here, we present a double layer technique that enables complete densification of a defect-free gadolinia-doped ceria diffusion barrier layer. In this approach, top and bottom layers were individually designed to perform unique functions based on systematic analysis of constrained sintering. The top layer, which contains 1 wt% CuO as a sintering aid, provides sufficient sintering driving force via liquid-phase sintering to allow complete densification of the film, while the bottom layer without a sintering aid prevents detrimental chemical reactions and regulates the global sintering rate to eliminate macro-defects. Such fabrication of dense diffusion barrier layers via a standard ceramic processing route would allow the use of novel cathode materials in practical SOFC manufacturing. Furthermore, the strategy presented in this study could be exploited in various multi-layer ceramic applications involving constrained sintering.     

Novel Niobium-Doped Titania Varistor with Added Barium and Bismuth

Characteristics of the sintered compacts and the microstructures and electrical properties of Nb-doped TiO₂ varistors with added Ba and Bi were studied at various sintering temperatures ranging from 1250° to 1400°C. Adding both Ba and Bi to Nb-doped TiO₂ ceramics resulted in a maximum intergranular phase and a minimum weight loss at 1350°C. In contrast, adding either Ba or Bi alone produced no such maxima and minima. The intergranular phases included mainly a Bi₂Ti₂O₇ crystal phase, apt to occur at a triple junction, and a Ba-rich amorphous phase that surrounded the grains, but discontinuously. The intergranular phases varied consistently with variation in electrical properties. The optimum conditions for the most efficient boundary barrier layer, with the lowest weight loss and the highest resistivity at low frequencies, were 1350°C with both Ba and Bi addition. The highest values for α (∼9.5), V_gb10 (∼0.8 V), and E_B (∼0.42 e V) support that finding. The effective relative dielectric constant, K _eff∼ 20 000, also was obtained under optimum conditions. The single addition of either Ba or Bi, however, produced nearly the opposite results, as discussed in this paper.     

Microstructural Design of Silicon Nitride with Improved Fracture Toughness: II, Effects of Yttria and Alumina Additives

Significant improvements in the fracture resistance of self-reinforced silicon nitride ceramics have been obtained by tailoring the chemistry of the intergranular amorphous phase. First, the overall microstructure of the material was controlled by incorporation of a fixed amount of elongated ß-Si₃N₄ seeds into the starting powder to regulate the size and fraction of the large reinforcing grains. With controlled microstructures, the interfacial debond strength between the reinforcement and the intergranular glass was optimized by varying the yttria-to-alumina ratio in the sintering additives. It was found that the steady-state fracture toughness value of these silicon nitrides increased with the Y:Al ratio of the oxide additives. The increased toughness was accompanied by a steeply rising R -curve and extensive interfacial debonding between the elongated ß-Si₃N₄ grains and the intergranular glassy phase. Microstructural analyses indicate that the different fracture behavior is related to the Al (and O) content in the ß´-SiAlON growth layer formed on the elongated ß-Si₃N₄ grains during densification. The results imply that the interfacial bond strength is a function of the extent of Al and Si bonding with N and O in the adjoining phases with an abrupt structural/chemical interface achieved by reducing the Al concentration in both the intergranular phase and the ß´-SiAlON growth layer. Analytical modeling revealed that the residual thermal expansion mismatch stress is not a dominant influence on the interfacial fracture behavior when a distinct ß´-SiAlON growth layer forms. It is concluded that the fracture resistance of self-reinforced silicon nitrides can be improved by optimizing the sintering additives employed.