SiBN ceramics are widely considered to be the most promising material for microwave-transparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant. This work focuses on the synthesis and ceramization of single-source precursors for the preparation of SiBN ceramics as well as the investigation of the corresponding microstructural evolution at high temperatures including molecular dynamic simulations. Carbon- and chlorine-free perhydropolysilazanes were reacted with borane dimethyl sulfide complex at different molar ratios to synthesize single-source precursors, which were subsequently pyrolyzed and annealed under N2 atmosphere (without ammonolysis) to prepare SiBN ceramics at 1100, 1200, and 1300 °C with high ceramic yield in contrast to previously widely-used ammonolysis synthesis process. The obtained amorphous SiBN ceramics were shown to have remarkably improved thermal stability and oxidation resistance compared to amorphous silicon nitride. Particularly, the experimental results have been combined with molecular dynamics simulation to further study the amorphous structure of SiBN and the atomic-scale diffusion behavior of Si, B, and N at 1300 °C. Incorporation of boron into the Si—N network is found to suppress the crystallization of the formed amorphous silicon nitride and hence improves its thermal stability in N2 atmosphere.

In the present work, bulk Si3N4/HfBxN1‐x ceramic nanocomposites were successfully fabricated via a polymer‐derived ceramic approach. The chemical reaction to form the single‐source precursor was confirmed by FT‐IR and XPS, in which both Si−H and N−H groups of perhydropolysilazane react with borane dimethyl sulfide complex and tetrakis(dimethylamido) hafnium(IV). The investigation of the polymer‐to‐ceramic transformation of the synthesized precursors indicates that Hf‐ and B‐modified PHPS exhibits high ceramic yields of up to 100 wt % after pyrolysis at 1000 °C under ammonia. Moreover, XRD and TEM results show that the SiHfBN ceramics with a molar ratio of B : Hf=5 and 10 resist crystallization at temperatures up to 1500 °C and separate after annealing at 1700 °C into nanocomposites comprising of an α‐Si3N4 matrix with embedded ternary HfBxN1‐x phases, solid solutions of rock salt‐type HfN and HfB. Based on the investigation, warm‐pressing was applied to fabricate bulk SiHfBN specimens, and the oxidation behavior of samples annealed at 1700 °C was recorded at 1500 °C over a range of oxidation times between 1 and 50 h. The weight changes of Si3N4/HfBxN1‐x ceramics with B : Hf molar ratios of 2 : 1, 5 : 1 and 10 : 1 are 4.31 %, 4.37 % and 2.57 %, respectively. The formation of HfSiO4, B2O3 and SiO2 during oxidation plays a crucial role for the improvement of the oxidation resistance of the Si3N4/HfBxN1‐x ceramics.

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