Oxygen vacancies as a link between the grain growth and grain boundary conductivity anomalies in titanium-rich strontium titanate

Titanium-rich (Sr/Ti?=?0.995) strontium titanate (ST) ceramics, air-sintered in a temperature range of 1400–1625?°C, were reported to possess anomalies in the grain growth and analogous anomalies in the grain boundary (GB) conductivity activation energy. However, these two interface-related phenomena, occurring at GBs, could not be associated with each other using a simple “brick-layer” model. In this work we revise the topic and advocate that the deviation from the model comes from the oxygen vacancies localized at GBs of the rapidly-cooled ST ceramics. To verify this, we annealed the ceramics in oxygen and performed their systematic and comparative analysis using impedance spectroscopy. A levelling-off in the GB conductivity activation energy, which increases for ≤1.24?eV, and a four-fold decrease in the GB permittivity are observed after annealing. Thus, we confirm a key role of oxygen vacancies in relation between the grain growth and GB conductivity anomalies of as-sintered Ti-rich ST ceramics.     

Significantly enhanced breakdown field in Ca1-xSrxCu3Ti4O12 ceramics by tailoring donor densities

Significantly enhanced breakdown field of 24.52 kV cm^?1 as well as noteworthy nonlinear coefficient of 8.11 and low dielectric loss of 0.077 were obtained in Ca_0.6Sr_0.4Cu₃Ti₄O₁₂ ceramic. It was proved from impedance spectra that improved breakdown field was attributed to enhanced grain boundary resistance and elevated Schottky barrier height, which was further found resulting from reduced donor densities in C-V measurements. In addition, it was found that the activation energy originated from oxygen vacancies was increased, indicating the generation of oxygen vacancies was suppressed. Since oxygen vacancies acted as donors in depletion layers, it is reasonable to deduce that the reduced donor density was mainly ascribed to the decreased oxygen vacancies. In conclusion, maximum integrated action of strong solid solution effect and weak Sr-stretching effect was achieved when Sr/Ca ratio is 40/60, leading to greatly elevated potential barrier height and enhanced breakdown field consequently.     

高频微振辅助工艺对激光焊接接头组织性能的影响

基于自主搭建的高频微振平台，进行316L不锈钢振动辅助激光焊接试验，探究高频微振激光焊接工艺对接头组织性能的影响. 结果表明，施加振动后，焊缝表面无飞溅，成形良好. 截面未出现塌陷、堆高，背部熔宽均匀. 振动的施加，能够明显细化焊缝区的晶粒，在共振频率1 467.5 Hz的高频微振激光焊条件下，晶粒尺寸最小. 点状颗粒物分布在奥氏体晶粒间，趋于弥散，新相及大颗粒物减少. 随着振动频率增加，焊缝区显微硬度值跟着增加，在较高共振频率显微硬度值增加显著，在共振频率1 467.5 Hz、加速度160 m/s2条件下，焊缝区平均硬度206 HV，与无振动相比，硬度值增加5.6%.     

Microstructural evolution and densification behavior of porous kaolin-based mullite ceramic added with MoO3

Microstructural evolution and densification behavior of porous kaolin-based mullite ceramic added with MoO₃ were investigated. The results indicated that MoO₃ addition not only lowered the secondary mullitization temperature to below 950?°C, but also facilitated effectively the anisotropic growth of mullite grains. Fine mullite whiskers grew and interlocked with one another in the pre-existing pore regions, in-situ forming a stiff 3D skeleton structure of mullite whiskers, which arrested further densification of the sample. On the other hand, due to the great capillary attraction of small pores, the liquid phase tended to spread over small grains, which favored the growth from small mullite grains into whiskers at the expense of the liquid phase. Consequently, competitive mechanisms of sintering and crystal growth of mullite functioned, which further limited the sample densification. As a result, the total linear shrinkage of the sample added with MoO₃ after firing at 1400?°C was only ??2.75%, and its porosity was retained at as high as 67%.     

Synergistic effect of binary fluoride sintering additives on the properties of silicon nitride ceramics

A variety of combinations of YF₃ and MgF₂ were used as sintering aids in the fabrication of Si₃N₄ ceramics via gas pressure sintering (GPS). The synergistic effects of YF₃ and MgF₂ on the liquid viscosity, mechanical properties, thermal conductivities, and grain growth kinetics of the Si₃N₄ ceramics were investigated. The results showed that appropriately adjusting the YF₃/MgF₂ ratio could decrease liquid viscosity, reducing the diffusion energy barrier of the solute atom and promoting mass transfer. Meanwhile, the chemical bonding strength in the grain boundary complexions formed by the metal cations also influenced grain boundary migration. Samples doped with 4 mol% YF₃ and 2 mol% MgF₂ achieved the lowest grain growth exponent (n = 2.9) and growth activation energy (Q = 616.7 ± 16.5 kJ mol^?1) as well as the highest thermal conductivity (83 W m^?1 K^?1) and fracture toughness (8.82 ± 0.13 MPa m^1/2).     

Introduction to crystallographic refinement of macromolecular atomic models

Refinement of atomic models is a necessary step in solving the macromolecular structure by X-ray diffraction methods. Nowadays, high automation and well-developed interfaces give a possibility to use the most popular refinement programs as black boxes. Nevertheless, working with complex objects requires an understanding of the internal structure and principles of operation of these programs and critical assessment of the results of refinement. In this review, we discuss the basic principles of the organization of refinement programs and the history of their improvement and development, as the studied objects became more and more complicated. The discussions are kept at the level of basic mathematic knowledge avoiding unnecessary formalism and too detailed expressions.     

Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

Zirconia-alumina multiphase ceramic fibers with exceptional thermal stability by melt-spinning from solid ceramic precursor

Zirconia-alumina multiphase ceramic fibers with 80 wt% (Z80A20 fiber) and 10 wt% (Z10A90 fiber) proportions of zirconia were prepared via melt-spinning and calcination from solid ceramic precursors synthesized by controllable hydrolysis of metallorganics. The zirconia-alumina multiphase fibers had a diameter of about 10 µm and were evenly distributed with alumina and zirconia grains. The Z80A20 and Z10A90 ceramic fibers had the highest filament tensile strength of 1.78 GPa and 1.87 GPa, respectively, with a peak value of 2.62 GPa and 2.71 GPa. The Z80A20 ceramic fiber has superior thermal stability compared to the Z10A90 ceramic fiber and a higher rate of filament strength retention due to the stability in grain size. After heat treatment at 1100 °C, 1200 °C, and 1300 °C for 1 h respectively, the filament tensile strength retention rate of Z80A20 ceramic fibers was 87 %, 80 %, and 40 %. While Z10A90 ceramic fiber was fragile after being heated at 1300 °C. The results showed that the high zirconia content facilitated the fiber's thermal stability.     

Hydrogen embrittlement and associated surface crack growth in fine-grained equiatomic CoCrFeMnNi high-entropy alloys with different annealing temperatures evaluated by tensile testing under in situ hydrogen charging

The effect of the annealing temperature after cold rolling on hydrogen embrittlement resistance was investigated with a face-centered cubic (FCC) equiatomic CoCrFeMnNi high-entropy alloy using tensile testing under electrochemical hydrogen charging. Decreasing annealing temperature from 800 °C to 750 °C decreased grain sizes from 3.2 to 2.1 μm, and resulted in the σ phase formation. Interestingly, the specimen annealed at 800 °C, which had coarser grains, showed a lower hydrogen embrittlement susceptibility than the specimen annealed at 750 °C, although hydrogen-assisted intergranular fracture was observed in both annealing conditions. Because the interface between the FCC matrix and σ was more susceptible to hydrogen than the grain boundary, the presence of the matrix/σ interface significantly assisted hydrogen-induced mechanical degradation. In terms of intergranular cracking, crack growth occurred via small crack initiation near a larger crack tip and subsequent crack coalescence, which has been observed in various steels and FCC alloys that contained hydrogen.