Excessive sintering shrinkage leads to severe deformation and cracking, affecting the microstructure and properties of porous ceramics. Therefore, reducing sintering shrinkage and achieving near‐net‐size forming is one of the effective ways to prepare high‐performance porous ceramics. Herein, low‐shrinkage porous mullite ceramics were prepared by foam‐gelcasting using kyanite as raw material and aluminum fluoride (AlF3) as additive, through volume expansion from phase transition and gas generated from the reaction. The effects of AlF3 content on the shrinkage, porosity, compressive strength, and thermal conductivity of mullite‐based porous ceramics were investigated. The results showed that with the increase of content, the sintering shrinkage decreased, the porosity increased, and mullite whiskers were produced. Porous mullite ceramics with 30 wt% AlF3 content exhibited a whisker structure with the lowest shrinkage of 3.5%, porosity of 85.2%, compressive strength of 3.06 ± 0.51 MPa, and thermal conductivity of 0.23 W/(m·K) at room temperature. The temperature difference between the front and back sides of the sample reached 710°C under high temperature fire resistance test. The low sintering shrinkage preparation process effectively reduces the subsequent processing cost, which is significant for the preparation of high‐performance porous ceramics.
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