High‐Pressure Synthesis of Amorphous Si₃N₄ and SiBN‐Based Monoliths without Sintering Additives

Amorphous Si₃N₄ and SiBN monoliths without sintering additives are successfully prepared by high‐pressure–low‐temperature (HPLT) sintering using the single‐source‐precursor‐derived amorphous Si₃N₄ and SiBN powders as raw materials. The microstructural evolution and crystallization behavior of the as‐prepared samples are investigated using scanning electron and transmission electron microscopy and X‐ray powder diffraction, respectively. The results show that the incorporation of boron in the Si–N network enhances the crystallization temperature up to 1200 °C. The Vickers’ hardness of the HPLT‐sintered Si₃N₄ sample amounts ≈11.6 GPa whether prepared at 1000 or 1200 °C, while the maximum hardness of the SiBN sample is up to 16.3 GPa. The fracture toughness of amorphous Si₃N₄ and SiBN5 samples is almost identical (around 2.5 MPa m^1/2) whether prepared at 1000 or 1200 °C, and SiBN2 and SiBN5 samples show an improved fracture toughness. In addition, the oxidation resistance of the as‐prepared samples is investigated at temperatures up to 1000 °C. A comparison between amorphous Si₃N₄ and SiBN monoliths demonstrates a positive effect of the presence of boron on their oxidation resistance.