Si3N4 ceramics are promising wave-transparent materials with excellent mechanical and dielectric properties. Vat photopolymerization (VPP) 3D printing provides a strategy for preparing ceramics with controllable complex structures. However, the difficulty in solidifying the slurry due to partial ultraviolet (UV) light absorption and high refractive index by the Si3N4 particles during the VPP process severely hampers the molding of Si3N4 ceramics. Higher laser power has to be used to increase the curing depth, which generates large internal stresses and leads to the warping of the samples. This paper presents a method to solve the warpage problem during VPP-3D printing using tributyl citrate as a plasticizer. The plasticizer can weaken the force between polymer molecular chains and reduce the internal stress of the green body. The warpage decreases gradually with the increase of tributyl citrate content, and the warpage decreases to 0 when the plasticizer content reaches 30 wt.% at high laser powers from 600 mW to 750 mW. Samples with different layer thicknesses were printed and the optimum thickness of 40 μm was obtained, at which the sintered Si3N4 samples possess a unique combination of mechanical properties, including a bending strength of 338.29±12.08 MPa, a fracture toughness of 6.94±0.11 MPa·m1/2 for the loading direction perpendicular and 5.37±0.99 MPa·m1/2 for the loading direction parallel to the build surface, respectively. The dielectric constant of all the samples is maintained in the range of 5.462 to 6.414. This work is expected to guide vat photopolymerization and the preparation of complex Si3N4 ceramic components.
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Rare earth (RE) silicate is one of the most promising environmental barrier coatings for silicon-based ceramics in gas turbine engines. However, calcium–magnesium–alumina–silicate (CMAS) corrosion becomes much more serious and is the critical challenge for RE silicate with the increasing operating temperature. Therefore, it is quite urgent to clarify the mechanism of high-temperature CMAS-induced degradation of RE silicate at relatively high temperatures. Herein, the interaction between RE2SiO5 and CMAS up to 1500 ℃ was investigated by a novel high-temperature in-situ observation method. High temperature promotes the growth of the main reaction product (Ca2RE8(SiO4)6O2) fast along the [001] direction, and the precipitation of short and horizontally distributed Ca2RE8(SiO4)6O2 grains was accelerated during the cooling process. The increased temperature increases the solubility of RE elements, decreases the viscosity of CMAS, and thus elevates the corrosion reaction rate, making RE2SiO5 fast interaction with CMAS and less affected by RE element species.