Vat photopolymerization (VPP) three-dimensional (3D) printing has emerged as a predominant technology for fabricating complex-shaped ceramic cores used in aeroengine hollow turbine blades. However, the inherent limitations of VPP 3D printing-fabricated silica-based cores, such as excessive sintering shrinkage and high-temperature deflection, have severely restricted their application in high-performance investment casting. In this study, we proposed a novel strategy to overcome this challenge by introducing kyanite into the silica-based ceramic core. The influence of kyanite content on microstructural evolution and comprehensive properties was systematically explored, and a ceramic core quality index (CQI) model was further established to evaluate the comprehensive performance. The results indicated that when the kyanite content exceeded 15 wt%, the volume expansion resulting from high-temperature decomposition effectively inhibited sintering shrinkage within the temperature range of 1300–1400 °C. Furthermore, the columnar mullite crystals generated from decomposition acted as the key factor enhancing the high-temperature performance. Optimal comprehensive properties, corresponding to a maximum CQI score of 78.85, were achieved with a kyanite content of 15 wt% and a sintering temperature of 1225 °C. Under this condition, the sintering shrinkage and casting shrinkage of ceramic cores were reduced to 3.06% and 0.86%, respectively. Additionally, the high-temperature deflection was significantly decreased to 0.82 mm, while the flexural strength and high-temperature flexural strength reached 10.06 and 27.05 MPa, respectively. This study provides a novel strategy for fabricating silica-based ceramic cores with lower sintering and casting shrinkage while elucidating the regulatory mechanism of kyanite on the core properties.
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It is well known that the grain size of high-entropy ceramics is quite small owing to the sluggish diffusion effect. However, abnormal grain growth often occurs in high-entropy pseudobrookite ceramics, ultimately resulting in the formation of many abnormally grown grains with a grain size as large as 50 μm. To study this phenomenon, the grain growth behavior of high-entropy pseudobrookite ceramics was systematically investigated in this paper. The results demonstrate that the starting material powders first react with each other to form a high-entropy intermediate phase and calcined TiO2 powders (TiO2-1100 °C), and then as the sintering temperature increases, the formed high-entropy intermediate phase further reacts with TiO2-1100 °C to form high-entropy pseudobrookite ceramics. Thus, in this system, in addition to the sluggish diffusion effect, the grain sizes of the high-entropy intermediate phase and TiO2-1100 °C also affect the morphology of high-entropy pseudobrookite. Compared to nanosized TiO2, micron-sized TiO2 has a lower sintering activity. Therefore, the high-entropy intermediate phases (Mg,Co,Ni,Zn)TiO3 and TiO2-1100 °C prepared with micron-sized starting materials exhibit lower grain sizes, finally resulting in the formation of high-entropy (Mg,Co,Ni,Zn)Ti2O5 with small grain sizes. Moreover, nano-indentation and thermal conductivity tests were carried out on high-entropy (Mg,Co,Ni,Zn)Ti2O5 with different morphologies. The results show that the hardness of high-entropy (Mg,Co,Ni,Zn)Ti2O5 increases from 6.05 to 9.95 GPa as the grain size increases, whereas the thermal conductivity decreases from 2.091±0.006 to 1.583±0.006 W·m−1·K−1. All these results indicate that high-entropy (Mg,Co,Ni,Zn)Ti2O5 with a small grain size is a potential material for thermal protection.
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As a type of titanate, the pseudobrookite (MTi2O5/M2TiO5) exhibits a low thermal expansion coefficient and thermal conductivity, as well as excellent dielectric and solar spectrum absorption properties. However, the pseudobrookite is unstable and prone to decomposing below 1200 ℃, which limits the practical application of the pseudobrookite. In this paper, the high-entropy pseudobrookite ceramic is synthesized for the first time. The pure high-entropy (Mg,Co,Ni,Zn)Ti2O5 with the pseudobrookite structure and the biphasic high-entropy ceramic composed of the high-entropy pseudobrookite (Cr,Mn,Fe,Al,Ga)2TiO5 and the high-entropy spinel (Cr,Mn,Fe,Al,Ga,Ti)3O4 are successfully prepared by the in-situ solid-phase reaction method. The comparison between the theoretical crystal structure of the pseudobrookite and the aberration-corrected scanning transmission electron microscopy (AC-STEM) images of high-entropy (Mg,Co,Ni,Zn)Ti2O5 shows that the metal ions (M and Ti ions) are disorderly distributed at the A site and the B site in high-entropy (Mg,Co,Ni,Zn)Ti2O5, leading to an unprecedentedly high configurational entropy of high-entropy (Mg,Co,Ni,Zn)Ti2O5. The bulk high-entropy (Mg,Co,Ni,Zn)Ti2O5 ceramics exhibit a low thermal expansion coefficient of 6.35×10−6 K−1 in the temperature range of 25–1400 ℃ and thermal conductivity of 1.840 W·m−1·K−1 at room temperature, as well as the excellent thermal stability at 200, 600, and 1400 ℃. Owing to these outstanding properties, high-entropy (Mg,Co,Ni,Zn)Ti2O5 is expected to be the promising candidate for high-temperature thermal insulation. This work has further extended the family of different crystal structures of high-entropy ceramics reported to date.
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