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In the processing of porous ceramics, shrinkage from green body to sintered compact during drying and sintering is one of the key concerns which affect microstructure and properties of porous ceramics. Through releasing gases from the burning of the pore forming agents, and volume expansion from the formation of low density resultants during sintering, the sintering shrinkage can be effectively compensated and near net size preparation can be achieved. Herein, near net size porous alumina‐calcium aluminate ceramics with controllable shrinkage have been prepared using a combination of gelcasting and pore‐forming agent process by adjusting the amount of CaCO3 and polymethyl methacrylate (PMMA) microspheres added. Al2O3 and CaCO3 were used as raw materials, PMMA microspheres were used as pore‐forming agent, isobutylene/maleic anhydride copolymer (Isobam104) was used as gelling agent and dispersing agent. The effects of the addition amounts of CaCO3 and PMMA in the slurry on the phase composition, shrinkage, porosity, and strength of porous alumina‐calcium aluminate ceramics were investigated. The results show that as the CaCO3 addition amount increases from 0 to 20 wt%, the shrinkage of the samples gradually decreases from 7.3% to −1.4%, and the consequent porosity increases from 58% to 66%, while the compressive strength increases from 5.9 to 15.5 MPa. When PMMA content increases from 10 to 50 wt%, the shrinkage of the samples decreases first and then increases, the porosity increases from 51% to 74%, and the compressive strength decreases from 12.5 to 5.3 MPa. The mechanisms for controlling shrinkages during preparation of porous alumina‐calcium aluminate ceramics can be attributed to the following aspects: on one hand, gas release from burning of PMMA and decomposition of CaCO3 during sintering; on the other hand, volume expansion due to the formation of lower density calcium aluminates which come from the reactions between CaO and Al2O3. The near net size preparation technique is of great significance for the manufacture of porous ceramics since the subsequent machining cost can be effectively reduced.

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Porous mullite matrix ceramics have excellent thermal and mechanical properties suitable for applications such as in thermal insulation. However, their applications are limited by processing defects from nonuniform sintering shrinkage and the trade-off between high porosity (preferred for low thermal conductivity) and high mechanical strength. Herein, we seek to minimize the sintering shrinkage by near-net-size preparation and improve the strength by in situ formed whisker network structure. Gelcasting forming technology and pressureless sintering were used to prepare porous mullite matrix ceramics using kyanite and α-Al 2 O 3 powders as the starting materials and using MoO 3 to promote the growth of mullite whiskers. The results showed that the sintering shrinkage could be compensated by the volume expansion from solid-state reaction during reaction sintering. The in situ formed three-dimensional (3D) whisker network further reduced sintering shrinkage and effectively improved the strength of the ceramics. An ultralow sintering shrinkage of .78% was achieved. The near-net-shape porous mullite matrix ceramics strengthened by 3D whisker network had a high porosity of 63.9%, a high compressive strength of 83.8 MPa and a high flexural strength of 53.5 MPa.