Ion migration behavior and its interaction with sintering environment in cation conductor during flash sintering

Flash sintering has been reported in various ceramics. Nevertheless, anion and cation conductors exhibit different flash-sintering behaviors, and the interaction mechanism between the conductive species and the sintering environment has remained unclear. Herein, we report the flash-sintering phenomena of a typical cation conductor, Na₃Zr₂(SiO₄)₂(PO₄) with anode region surrounded by air and NaNO₃ environments. The results prove that the ionic behavior and joule heating distribution can be controlled by changing the electrode environment. Four possible scenarios describing the ion migration behavior and interaction with the environment are proposed for providing a guidance for controlling the ion interaction behavior during flash sintering.     

Dense and core-rim structured B4C-TiB2 ceramics with Mo-Co-WC additive

B₄C-TiB₂ ceramics (TiB₂ ranging 5~70 vol%) with Mo-Co-WC as the sintering additive were prepared by spark plasma sintering. In comparison with B₄C-TiB₂ without additive, the enhanced densification was evident in the sintered specimen with Mo-Co-WC additive. Core-rim structured grain was observed around TiB₂ grains. The interface of the rim between TiB₂ and B₄C phases demonstrated different feature: the inner borderline of the rim exhibited a smooth feature, whereas a sharp curved grain boundary was observed between the rim and the B₄C grain. The formation mechanism is discussed: the epitaxial growth of (Ti,Mo,W)B₂ rim around the TiB₂ core may occur as a result of the solid solution and dissolution-precipitation between TiB₂ phase and the sintering additive. It was revealed that the fracture toughness increased as the content of TiB₂ content increased, alongside the decreased hardness. B₄C-30 vol% TiB₂ specimen demonstrated the optimal combination of mechanical properties, reaching Vickers hardness of 24.3 GPa and fracture toughness of 3.33 MPa·m^1/2.     

Microstructure and mechanical properties of α/β-Si3N4 composite ceramics with novel ternary additives prepared via spark plasma sintering

In this study, α/β-Si₃N₄ composite ceramics with high hardness and toughness were fabricated by adopting two different novel ternary additives, ZrN–AlN–Al₂O₃/Y₂O₃, and spark plasma sintering at 1550 °C under 40 MPa. The phase composition, microstructure, grain distribution, crack propagation process and mechanical properties of sintered bulk were investigated. Results demonstrated that the sintered α/β-Si₃N₄ composite ceramics with ZrN–AlN–Al₂O₃ contained the most α phase, which resulted in a maximum Vickers hardness of 18.41 ± 0.31 GPa. In the α/β-Si₃N₄ composite ceramics with ZrN–AlN–Y₂O₃ additives, Zr₃AlN MAX-phase and ZrO phase were found and their formation mechanisms were explained. The fracture appearance presented coarser elongated β-Si₃N₄ grains and denser microstructure when 20 wt% TiC particles were mixed into Si₃N₄ matrix, meanwhile, exhibited maximum mean grain diameter of 0.98 ± 0.24 μm. As a result, the compact α/β-Si₃N₄ composite ceramics containing ZrN–AlN–Y₂O₃ additives and TiC particles displayed the optimal bending strength and fracture toughness of 822.63 ± 28.75 MPa and 8.53 ± 0.21 MPa?m^1/2, respectively. Moreover, the synergistic toughening of rod-like β-Si₃N₄ grains and TiC reinforced particles revealed the beneficial effect on the enhanced fracture toughness of Si₃N₄ ceramic matrix.     

A thermal perspective of flash sintering: The effect of AC current ramp rate on microstructure evolution

In flash sintering experiments, the thermal history of the sample is key to understanding the mechanisms underlying densification rate and final properties. By combining robust temperature measurements with current-ramp-rate control, this study examined the effects of the thermal profile on the flash sintering of yttria-stabilized zirconia, with experiments ranging from a few seconds to several hours. The final density was maximized at slower heating rates, although processes slower than a certain threshold led to grain growth. The amount of grain growth observed was comparable to a similar conventional thermal process. The bulk electrical conductivity correlated with the maximum temperature and cooling rate. The only property that exhibited behavior that could not be attributed to solely the thermal profile was the grain boundary conductivity, which was consistently higher than conventional in flash sintered samples. These results suggest that, during flash sintering, athermal electric field effects are relegated to the grain boundary.     

Grain size effect on microwave dielectric properties of Na2WO4 ceramics prepared by cold sintering process

In this work, cold sintering was adopted to prepare Na₂WO₄ ceramics with different grain sizes ranging from 0.632 μm to 17.825 μm. Their microstructures, complex impedance, and microwave dielectric properties were studied in-depth. It was found that samples with relative densities higher than 92% can be successfully synthesized by cold sintering process at a low temperature of 240 °C. However, their electrical properties have strong dependence on the grain size. Specifically, the resistance of grain boundaries decreases dramatically with the increase of grain sizes, while the quality factor has a positive correlation with the grain sizes of Na₂WO₄ ceramics. Excellent microwave dielectric properties, including permittivity = 5.80, Q × f = 22,000 GHz, and TCF = −70 ppm/°C, are obtained for Na₂WO₄ ceramics with a grain size of 4.477 μm prepared by cold sintering process.     

Resistance reduction effect of potassium bismuth titanate doping in yttrium–manganese co-doped medium Curie temperature barium titanate lead free ceramics through improved synthesis process

Through improved synthesis process, resistance reduction effect of (K_0.5Bi_0.5)TiO₃ (KBT) doping in Y–Mn co-doped BaTiO₃ (BT) lead free ceramics was investigated. By different doping methods (doping K₂O, Bi₂O₃ and TiO₂ or synthesized KBT), medium Curie temperature (around 130 °C) lead free BT ceramics were obtained with ultra-low resistivity (13.84 Ωcm) with a temperature maintaining process at 700 °C. In this contribution, effect of sintering process and doping methods is discussed in detail.     

A novel combination of precursor pyrolysis assisted sintering and rapid sintering for construction of multi-composition coatings to improve ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites

A double-layer coating composed of MoSi₂–SiO₂–SiC/ZrB₂–MoSi₂–SiC was designed and successfully constructed by a novel combination of precursor pyrolysis assisted sintering and rapid sintering to improve the ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites (CSs). The ZrB₂–MoSi₂–SiC inner layer coating was in relatively uniform distribution in the zone of 0–3 mm from the surface of CSs through the slurry/precursor infiltration in vacuum and SiOC precursor pyrolysis assisted sintering, which played a predominant role in improving oxidation and ablation resistance and maintaining the morphology of CSs. The MoSi₂–SiO₂–SiC outer layer coating was prepared by the spray and rapid sintering to further protect CSs from high-temperature oxidation. The ablation resistance of CSs coated with double-layer coating was evaluated by an oxygen-acetylene ablation test under the temperature of 1600–1800 °C with different ablation time of 1000 and 1500 s. The results revealed that the mass recession rates increased with the rise of ablation temperature and extension of ablation time, ranging from 0.47 g/(m²·s) to 0.98 g/(m²·s) at 1600–1800 °C for 1000 s and from 0.72 g/(m²·s) to 0.86 g/(m²·s) for 1000–1500 s at 1700 °C, while the linear recession rates showed negative values at 1700 °C due to the formation of oxides, such as SiO₂ and ZrO₂. The ablation mechanism of the double-layer coating was analyzed and found that a SiO₂–ZrO₂–Mo_4.8Si₃C_0.6 oxidation protection barrier would be formed during the ablation process to prevent the oxygen diffusion into the interior CSs, and this study provided a novel and effective way to fabricate high-temperature oxidation protective and ablation resistant coating.     

锂辉石-氧化钙烧结法提锂的物相重构与动力学

对锂辉石-氧化钙烧结过程进行热力学分析，绘制了各反应Gibbs自由能与温度的关系图。结果表明，Al₂O₃会优先和Na₂O、Li₂O、K₂O反应，然后与CaO反应生成CaO·Al₂O₃，而且烧结温度需高于1060℃以保证LiAlSi₂O₆能够完成晶形转变。并探讨了锂辉石-氧化钙烧结法提锂的反应机理。考察了不同烧结条件对锂浸出率的影响并对熟料进行X射线衍射（XRD）分析表征。实验结果表明，在配料比为1∶1.25、烧结温度1150℃、烧结时间60min时，锂的浸出率达到92.14%，熟料中的主要物相为Ca₂SiO₄与LiAlO₂。利用XRD和扫描电镜-能谱联用仪（SEM-EDS）对熟料与浸出渣的物相、显微形貌及元素分布情况进行了分析表征。为了确定烧结反应的控制性步骤，在最优烧结条件的基础上对烧结过程进行动力学分析，结果表明，锂辉石-氧化钙烧结体系属于球形颗粒三维界面化学反应控制，烧结过程的动力学拟合方程为\mathrm{1}-{(\mathrm{1}-x)}^{\mathrm{1}/\mathrm{3}}=\mathrm{0.00677}t。     

Low-temperature hot-press sintering of AlN ceramics with MgO–CaO–Al2O3–SiO2 glass additives for ceramic heater applications

Aluminum nitride (AlN) is used a ceramic heater material for the semiconductor industry. Because extremely high temperatures are required to achieve dense AlN components, sintering aids such as Y₂O₃ are typically added to reduce the sintering temperature and time. To further reduce the sintering temperature, in this study, a low-melting-temperature glass (MgO–CaO–Al₂O₃–SiO₂; MCAS) was used as a sintering additive for AlN. With MCAS addition, fully dense AlN was obtained by hot-press sintering at 1500 °C for 3 h at 30 MPa. The mechanical properties, thermal conductivity, and volume resistance of the sintered AlN–MCAS sample were evaluated and compared with those of a reference sample (AlN prepared with 5 wt% Y2O3 sintering aid sintered at 1750 °C for 8 h at 10 MPa). The thermal conductivity of AlN prepared with 0.5 wt% MCAS was 91.2 W/m?K, which was 84.8 W/m?K lower than that of the reference sample at 25 °C; however, the difference in thermal conductivity between the samples was only 14.2 W/m?K at the ceramic-heater operating temperature of 500 °C. The flexural strength of AlN–MCAS was 550 MPa, which was higher than that of the reference sample (425 MPa); this was attributed to the smaller grain size achieved by low-temperature sintering. The volume resistance of AlN–MCAS was lower than that of the reference sample in the range of 200–400 °C. However, the resistivity of the proposed AlN–MCAS sample was higher than that of the reference sample (500 °C) owing to grain-boundary scattering of phonons. In summary, the proposed sintering strategy produces AlN materials for heater applications with low production cost, while achieving the properties required by the semiconductor industry.