Fine-diameter Si–B–C–N ceramic fibers enabled by polyborosilazanes with N–methyl pendant group

Given the superior thermal stability and electromagnetic features, continuous Si–B–(C)–N ceramic fibers have displayed great potential to fulfill the increasing demand for the high-temperature structural and functional materials. Manufacture of such ceramic fibers depends heavily upon the design of processable polymer precursors. Herein, a class of polyborosilazanes (PBSZs) with high spinnability were created through a facile one-pot synthesis. The trade-off between spinnability and ceramic yield of PBSZs was overcome by using heptamethyldisilazane and hexamethyldisilazane as the co-condensing agents to polymerize silicon and boron chloride monomers. The optimal PBSZs can fabricate continuous Si–B–C–N fibers with homogeneous diameter of 7.9 ± 0.5 μm and high ceramic yield of 80 wt%. Experimental characterization and quantum chemical computation revealed the mechanistic pictures of the impact of pendant groups on the polycondensation, melt spinning, and pyrolyzing process. These insights improve our understanding of spinnable pre-ceramic polymers for exploiting high-performance nitride ceramic fibers.