Dislocation toughening in single-crystal KNbO3

The growing research interest in dislocation-tuned functionality in ceramics is evident, with the most recent proofs-of-concept for enhanced ferroelectric properties, electrical conductivity, and superconductivity via dislocations. In this work, we focus on dislocation-tuned mechanical properties and demonstrate that, by engineering high dislocation densities (up to 10¹⁴ m⁻²) into KNbO₃ at room temperature, the fracture toughness can be improved by a factor of 2.8. The microstructures, including dislocations and domain walls, are examined by optical microscopy, electron channeling contrast imaging, piezo-response force microscopy, and transmission electron microscopy methods to shed light on the toughening mechanisms. In addition, high-temperature (above the Curie temperature of KNbO₃) indentation tests were performed to exclude the influence of ferroelastic toughening, such that the origin of the toughening effect is pinpointed to be dislocations.     

The influence of hafnium removal on the microstructure and properties of 8YSZ ceramics

The effects of hafnium removal on the sinterability, phase composition, and microstructural, mechanical, and electrical properties of 8YSZ (8 mol% yttrium stabilized zirconia) were investigated using SEM, XRD, Raman spectroscopy, EBSD, three-point bending, Vickers indentation, and impedance spectroscopy. The 8YSZ and 8YSZ₀ (8 mol% yttrium-stabilized hafnium-free zirconia) ceramics were prepared via dry pressing and atmospheric sintering, respectively. The overall mechanical properties of the 8YSZ₀ ceramic were poor. However, at a sintering temperature of 1450°C, the relative density of 8YSZ and 8YSZ₀ ceramics was almost identical. 8YSZ₀ had a slightly smaller grain size and activation energy, and its electrical properties were slightly better than those of the 8YSZ ceramics. The presence of tetragonal secondary phases in the cubic structure of 8YSZ ceramics inhibited crack propagation and led to an increase in the mechanical properties and a decrease in the ion conductivity. In terms of the crystal structure, the increase in the cubic phase lattice parameters and tetragonal phase c/a values of the 8YSZ₀ ceramics was attributed to the larger Zr⁴⁺radius, reduced local lattice distortion, and increased matrix oxygen vacancy concentration and cubic phase content. The EBSD analysis results indicated that there was no significant difference in grain orientation between the two types of ceramics, but the content of 8YSZ ceramics in large angle grain boundaries was slightly higher, especially in special grain boundaries Σ3 and Σ9. Therefore, this material can be used as a solid-state electrolyte candidate.     

Electrical conduction mechanisms and effect of atmosphere annealing on the electrical properties of BiFeO3-BaTiO3 ceramics

BiFeO₃-BaTiO₃ (BFBT) is a promising high temperature piezoelectric ceramic system, as it possesses both high electromechanical properties and high Curie temperature. However, pure BFBT commonly exhibits large electrical conductivity at high temperatures, and there is considerable disagreement on its electrical conduction mechanism. Here we investigated the electrical conduction mechanisms of 0.70BiFeO₃-0.30BaTiO₃ and 0.67BiFeO₃-0.33BaTiO₃ ceramics by systematic impedance spectroscopy measurements as a function of oxygen partial pressure and temperature. Both ceramics exhibit higher electrical conductivity with an increase of oxygen partial pressure, consistent with p-type semiconductor behaviors. Particularly, reduced conductivity and improved ferroelectric remanent polarization can be obtained in BFBT when annealed in inert atmosphere. This study provides fundamental basis for preparing insulating and high performance BFBT ceramics.     

莫来石陶瓷中的位错及其对力学性能的影响

利用透射电镜对莫来石陶瓷中位错的组态进行观察，结果表明，莫来石陶瓷中的位错易被第二相钉扎，两列位错遇易发生反应，全位错易分解成偏位错，并扩展形成层错。这说明，即使是脆性材料，其位错在一定条件下仍然是可动的。本文认为，位错在常温和高温条件下莫来石陶瓷力学性能影响不同，并从位错的角度解释了莫来石陶瓷力学性能的特点，提出改进材料制备工艺的途径。     

Electrical conductivity of YSZ-SDC composite solid electrolyte synthesized via glycine-nitrate method

Yttria-stabilized zirconia (YSZ) is a common solid electrolyte for solid oxide fuel cells (SOFCs) because of its high electrical conductivity and high ionic transference number in both oxidizing and reducing atmospheres. Samarium doped ceria (SDC) has also been considered as an alternative electrolyte material to YSZ for intermediate temperature SOFC because of its high conductivity at relatively low temperatures. Due to improved ionic conductivity of YSZ at high temperature (~ 800 °C) and good conductivity of SDC in the intermediate temperature range (600–800 °C), the electrical properties of YSZ-SDC composites were investigated. Composites of YSZ and SDC with weight ratio 9.5:0.5, 9:1 and 8.5:1.5 were synthesized via glycine-nitrate route. XRD pattern of the systems revealed the formation of composite phases. Biphasic electrolyte microstructures were observed, in which SDC grains are dispersed in YSZ matrix. Relative density of the compositions was found to be more than 92% to the theoretical density. It was observed that the interface provides a channel for ionic transport, leading to a notable ionic conductivity. With increase in SDC weight ratio the electrical conductivity was found to increase. For weight ratio 8.5:1.5 the electrical conductivity was found to be greater than that of YSZ in the temperature range 400–700 °C. Further, for weight ratio more than 8.5:1.5, conductivity was found to decreases due to the formation of a few other insulating impurity phases. The electrode polarisation was also found to reduce significantly with SDC in the composite electrolyte system. Thus, such composite system may be useful for improving the ionic conductivity of the composite electrolytes.     

Porous YSZ ceramics with unidirectionally aligned pore channel structure: Lowering thermal conductivity by silica aerogels impregnation

The previous report of this work has demonstrated the fabrication and properties of porous yttria-stabilized zirconia (YSZ) ceramics with unidirectionally aligned pore channels. As a follow-up study, the present work aims at lowering the thermal conductivity of the porous YSZ ceramics by silica aerogels impregnation. The porous YSZ ceramics were immersed in an about-to-gel silica sol. Both the unidirectionally aligned pore channels and the inter-grain pores by grain stacking in the channel-pore wall of the porous YSZ ceramics were impregnated with the silica sol. After aging and supercritical drying, silica aerogels formed in the macroporous network of the porous YSZ ceramics with unidirectionally aligned pore channels. The influences of silica aerogel impregnation on the microstructure and properties of porous YSZ ceramics with unidirectional aligned pore channels were investigated. The porosity decreased after impregnation with silica aerogels. Both microstructure observation and pore size distribution indicated that both channel-pore size and inter-grain pore-size decreased significantly after impregnation with silica aerogels. Impregnating porous YSZ ceramics with silica aerogels remarkably lowered the room-temperature thermal conductivity and enhanced the compressive strength. The as-fabricated materials are thus suitable for applications in bulk thermal isolators.     

Nucleation and Growth of Inversion Domains in AIN: Part I, Study of Fundamental Processes

Inversion domains (IDs) are frequently observed in sintered AIN ceramics. In the present study, different stages of ID formation and growth were analyzed by transmission electron microscopy. A model was derived to describe the mechanisms of ID nucleation, growth, and interaction with dislocations. Accordingly, IDs are nucleated by wide inverted dislocation dissociations. Preexisting dislocations interact with moving ID boundaries (IDBs) by a mechanism of dissociation and integration into the IDE. The defect structures at IDBs are characterized by the inversion, a translation R = 1/3(1 1 00) corresponding to Shockley partials, and a translation R = w·[0001] perpendicular to the basal plane. The results are fundamental for further experiments of artificial generation or annihilation of IDs.     

亚微米晶粒氧化钇稳定氧化锆电解质的稳定性

氧化钇稳定氧化锆(yttria-stabilized zirconia,YSZ)是目前使用最多的电解质材料,YSZ结构和性能的长期稳定对固体氧化物燃料电池(solid oxide full cell,SOFC)系统的可靠性至关重要。重点研究了具有亚微米结构的YSZ在850℃环境中的长期老化性能,结果发现:在850℃空气气氛中老化处理300h后,YSZ中小于1μm的部分晶粒出现了继续生长的现象,使得小于1μm晶粒比例下降10%～20%;当这部分晶粒长大到1～2μm,呈现稳定状态,即没有出现晶粒的过分长大;老化600h和1000h后,小晶粒(小于1μm)所占比例几乎不变。伴随着晶粒尺寸分布变化,YSZ电解质的电导率也比老化处理初期(300h)有所降低;当老化处理600h后,电导率下降趋势变缓;老化处理1000h后,电导率基本稳定,且1000℃电导率仍然保持在0.15S/cm以上。电导率下降主要是由YSZ晶粒部分长大引起的。具有上述性能的YSZ用作SOFC电解质可以满足长期使用的要求。     

Structure and properties of Al2O3-bonded porous fibrous YSZ ceramics fabricated by aqueous gel-casting

To meet requirements for high porosity and high strength, novel aqueous gel-casting process has been successfully developed to fabricate Al₂O₃-bonded porous fibrous YSZ ceramics with ρ-Al₂O₃ and YSZ fibers as raw materials. Microstructure, phase composition, apparent porosity, bulk density, thermal conductivity, and compressive strength of fabricated porous ceramics were investigated, and effects of fiber content on properties were discussed. According to results, bird nest 3D mesh with interlaced YSZ fibers and Al₂O₃ binder was formed, ensuring the ability to obtain high performance, lightweight ceramics. An increase in the number of YSZ fibers led to more complex interlaced arrangement of fibers and denser network structure of porous ceramics at retaining their stability. Furthermore, their apparent porosity and bulk density increased, whereas thermal conductivity and compressive strength decreased with increasing the fiber content. In particular, comparatively high porosity (71.1–72.7%), low thermal conductivity (0.209–0.503 W/mK), and relatively high compressive strength (3.45–4.24 MPa) were obtained for as-prepared porous ceramics, making them promising for applications in filters, thermal insulation materials, and separation membranes.     

Effect of hot-pressing sintering on thermal and electrical properties of AlN ceramics with impedance spectroscopy and dielectric relaxations analysis

The effects of hot-pressing sintering on the phase composition, microstructure, thermal and electrical properties of AlN ceramics with CeO₂–CeF₃ additives were studied. During hot-pressing sintering, high pressure reduced the grain boundary phase CeAlO₃ and decreased the concentration of oxygen in AlN ceramics. The hot-pressing sintered AlN samples had a much higher thermal conductivity of 191.9 W/m·K than pressureless sintered ones because of the great reduction of grain boundary phases and oxygen impurities in AlN ceramic. As the carbon content in hot-pressing sintered sample was very high, carbon contamination led to the decrease in electrical resistivity and changes in polarization mechanisms for AlN ceramics. The relaxation peak in the dielectric temperature spectrum with an activation energy of 0.64 eV for hot-pressing sintered samples was caused by electrons from free carbon at low temperature. Overall, hot-pressing sintering can effectively increase the thermal conductivity and change the electrical properties of AlN ceramics.     

Excess oxygen-vacancy formed by FAST regime of direct-current electric field during flash sintering for 3 mol%–10 mol% Y2O3-doped ZrO2

The amount of excess oxygen vacancies that are generated during FAST regime of direct-current flash sintering was estimated semi-quantitatively for 3 mol%–10 mol% Y₂O₃-doped ZrO₂ (3–10YSZ) using the temperature dependence of the electrical conductivity. For the estimation, the electrical conductivity in the temperature range, where shrinkages are below a few percent, was used to avoid the effect of large microstructural changes on the electric conductivity. For all Y₂O₃ contents except 3YSZ, the amount of excess oxygen vacancies increased above a compact temperature of approximately 840 °C, which depended on Y₂O₃ content, and was highest in 8YSZ. Approximately 0.13% excess oxygen vacancy was generated by direct-current flashing in 8YSZ in the present electric field condition. In contrast, the increase in the excess oxygen vacancies is negligible in 3YSZ. The dependence of the amount of excess oxygen vacancies on the Y₂O₃ content was related possibly to the dependence of the electrode overvoltage on the Y₂O₃ content.     

Mechanical properties,oxygen barrier property,and chemical stability of RE3NbO7 for thermal barrier coating

Rare earth niobate (RE₃NbO₇, RE = Dy, Y, Er, Yb) ceramics have shown extremely low thermal conductivity but remain questionable in high temperature thermal barrier coating (TBC) applications with high thermal, mechanical, and chemical loads. Herein, we comprehensively characterize the properties of rare earth niobates, including mechanical properties, oxygen barrier properties, chemical stability, etc. It is found that the oxygen conductivities of the rare earth niobates are three orders of magnitude lower than 7wt.% yttria-stabilized zirconia (YSZ), indicating a remarkable oxygen barrier property to avoid oxidation of underlying metallic components. The corrosion resistance of rare earth niobate against calcium-magnesium-aluminum silicate (CMAS) is also significantly better than that of YSZ. Together with the extremely low thermal conductivity, the rare earth niobates exhibit a combination of excellent high temperature properties, which may become a promising candidate material of high temperature TBC of next generation gas turbines.     

High-pressure sintered yttria stabilized zirconia ceramics

Fast densification of 8YSZ ceramics under a high pressure of 4.5 GPa was carried out at different temperatures (800, 1000, 1450 °C), by which a high relative density above 92% could be obtained. FT-Raman spectra indicate that the 8YSZ underwent a phase transition from partially tetragonal to partially cubic phase as temperatures increase from 1000 to 1450 °C when sintering under high pressure. The electrical properties of the samples under different high-pressure sintering conditions were measured by complex impedance method. The total conductivity of 0.92 × 10⁻² S cm⁻¹ at 800 °C has been obtained for 8YSZ under high pressure at 1450 °C, which is about 200 °C lower than that of the samples prepared by conventional pressureless sintering.     

新型层状陶瓷Ti3SiC2的研究进展

新型层状陶瓷Ti3SiC2兼有金属和陶瓷的许多优良性能，具有高的热导率和电导率，易加工，同时具有良好的抗热震性、抗氧化性和高温稳定性。本文从层状陶瓷Ti3SiC2制备方法、结构和性能等方面进行综述，并对其应用前景进行展望。     

新型层状陶瓷Ti3SiC2的研究进展

新型层状陶瓷Ti3SiC2兼有金属和陶瓷的许多优良性能,具有高的热导率和电导率,易加工,同时具有良好的抗热震性、抗氧化性和高温稳定性.本文从层状陶瓷Ti3SiC2制备方法、结构和性能等方面进行综述,并对其应用前景进行展望.     

Development of a Novel Ceramic Support Layer for Planar Solid Oxide Cells

The conventional solid oxide cell is based on a Ni–YSZ support layer, placed on the fuel side of the cell, also known as the anode supported SOFC. An alternative design, based on a support of porous 3YSZ (3 mol.% Y₂O₃–doped ZrO₂), placed on the oxygen electrode side of the cell, is proposed. Electronic conductivity in the 3YSZ support is obtained post sintering by infiltrating LSC (La_0.6Sr_0.4Co_1.05O₃). The potential advantages of the proposed design is a strong cell, due to the base of a strong ceramic material (3YSZ is a partially stabilized zirconia), and that the LSC infiltration of the support can be done simultaneously with forming the oxygen electrode, since some of the best performing oxygen electrodes are based on infiltrated LSC. The potential of the proposed structure was investigated by testing the mechanical and electrical properties of the support layer. Comparable strength properties to the conventional Ni/YSZ support were seen, and sufficient and fairly stable conductivity of LSC infiltrated 3YSZ was observed. The conductivity of 8–15 S cm^–1 at 850 °C seen for over 600 h, corresponds to a serial resistance of less than 3.5 m Ω cm² of a 300 μm thick support layer.     

Investigation on the phase stability of yttria-stabilized zirconia electrolytes for high-temperature electrochemical application

For the Fundamental studies on the phase stability of YSZ, we tried to approach the detailed influences of practical conditions through various hypotheses. The phase stability of cubic and tetragonal yttria-stabilized zirconia (YSZ) was studied in the specific electrochemical conditions of current loading and molten salt flux. The degradation of electrochemical performance in the cubic phase occurred more easily than in the tetragonal phase because of yttrium elution in the lattice. The fully stabilized cubic phase showed high electrical performance as an oxide ion-conducting electrolyte, but phase decomposition occurred more easily under applied currents or chemical loading conditions than for the partially stabilized tetragonal phase. When YSZ reacted with a molten salt fluoride flux in solid oxide membrane (SOM) processing, which is used for direct metal reduction, and high-temperature electrolysis in the molten salt, the electrical conductivity of cubic YSZ was decreased by ~37%, while that of tetragonal YSZ showed no change. Our findings have important implications for the use of YSZ as an oxygen conductor in various electrochemical devices.     

Ti3SiC2陶瓷粉末的制备

新型层状陶瓷材料Ti3SiC2集金属和陶瓷的优良性能于一身,如低密度、高熔点、良好的导电导热性、高弹性模量、高断裂韧性、耐氧化、耐热震、易加工且有良好的自润滑性。在高温结构陶瓷、电刷和电极材料、可加工陶瓷材料、自润滑材料等领域有着广泛的应用前景。本文综合介绍了Ti3SiC2粉求制备的研究进展。最近,作者以Ti／Si／C／Al元素粉为原料,采用无压烧结的方法制备出纯度较高的Ti3SiC2陶瓷粉末。为Ti3SiC2基复合材料的发展开辟了一条新途径。     

Precipitation induced crack healing in a Ti2SnC ceramic in vacuum

Self-healing ceramics are able to heal cracks through an oxidative healing mechanism at high temperature in oxidizing environments with the recovery of original performance and functionality. However, the oxidation induced repair may be impossible when the ceramics are used in vacuum or inert atmospheres with low oxygen partial pressures. So far little work has been done on crack healing in vacuum or inert atmospheres. Here we report on the crack healing of a Ti₂SnC ceramic in vacuum by a precipitation induced repair mechanism. Cracks induced by thermal shock in Ti₂SnC are completely filled by only metallic Sn at temperatures above 800 °C for only 1 h in vacuum. The electrical conductivity of healed materials is fully recovered, and it even exceeds the initial conductivity. This work might bring a new wave of research on crack healing behavior of ceramics in low oxygen partial pressure environments.     

Dislocation-Related Plasticity of Ceria-Stabilized Zirconia Polycrystals

Much higher plastic strain of 4% in Ce-TZP ceramics was produced by a novel thermal-mechanical process below 450°C. Observation by TEM showed that there were abundant dislocation pile-ups associated with a few martensitic laths in the deformed samples. The density of dislocations increased with thermal-mechanical cycles. These suggested that dislocation multiplication was caused by the high local stress concentration in front of a martensitic lath during the thermal-mechanical deformation. The generation and movement of dislocations introduced extra plasticity beside the transformation plasticity caused by martensite. Meanwhile, movement of dislocations relaxes the interface stress at martensitic laths to prevent reverse martensitic transformation and early cracking of the specimens. The results are discussed in terms of thermal-mechanical action and dislocation multiplication.