A novel approach to the preparation of porous polysilazane-derived ceramics is presented, combining non-aqueous solidification templating (freeze casting) of a liquid preceramic polymer with a photo-induced thiol-ene “click” reaction at temperatures below −10 °C. Upon directional solidification of the reaction mixture consisting of the preceramic polymer, a quaternary thiol, a photoinitiator, and camphene as pore-structuring agent, low-temperature photopolymerization of the preceramic polymer was achieved by irradiation with visible light, its feasibility demonstrated by photorheology. Effects of the polymer/structuring agent ratio and the solidification rate on porosity and pore morphology were evaluated using porosimetry and tomography techniques. The structural features were set in relation to mechanical properties, showing compressive strengths up to 74 MPa at porosities between 58% and 76%.

This new processing technique facilitates the generation of polysilazane-derived ceramics with highly tailorable pore structures, with prospective uses in processes ranging from membrane-based separation to catalysis.

提出了一种新颖的制备多孔聚硅氮烷衍生陶瓷的方法，该方法将液态预陶瓷聚合物的非水固化模板（冻结浇铸）与低于-10°C的光诱导硫醇-烯“点击”反应结合在一起。在由预陶瓷聚合物，季硫醇，光引发剂和作为孔结构剂的camp烯组成的反应混合物定向固化后，通过可见光照射实现了预陶瓷聚合物的低温光聚合，其可行性由光流变学证明。使用孔隙率法和层析成像技术评估了聚合物/结构剂比例和固化速率对孔隙率和孔隙形态的影响。根据机械性能设置结构特征，

这项新的加工技术促进了具有高度可调节孔结构的聚硅氮烷衍生陶瓷的生产，并有望用于从基于膜的分离到催化的过程中。