Fabrication of dense SiBCN monolith at a lower temperature and its high-temperature performance

In this study,a crack-free pyrolysis process of partially cured precursor powder compacts was developed to prepare dense silicon boron carbonitride(SiBCN)monoliths at much lower temperatures(1300℃),thereby circumventing the challenges of sintering densification(>1800℃).Unlike the elastic fracture in over-cured precursors or the viscoelastic deformation in under-cured precursors,the partially cured precursor,exhibiting elastic-plastic deformation behavior,facilitates limited nanoscale pore formation in a dense structure,achieving a balance between crack-free pyrolysis and densification.Compared to SiBCN derived from the over-cured precursor(σ=~159 MPa,K_(IC)=1.9 MPa:m^(1/2),Vickers hardness(HV)=7.8 GPa,and E=122 GPa),the resulting SiBCN monolith exhibited significantly improved mechanical properties(σ=~304 MPa,K_(IC)=3.7 MPa-m12,HV=10.6 GPa,and E=161 GPa)and oxidation resistance.In addition,this study investigated the high-temperature performance of SiBCN monoliths,including crystallization and oxidation,and determined the oxidation kinetics induced by pore structure healing and the different oxidation mechanisms of Si-C-N and B-C-N clusters in the amorphous structure.Due to its unique composition and structure,the SiBCN ceramic oxide layer exhibits exceptional self-healing effects on repairing the nanoporous system in the initial stage and shows outstanding high-temperature stability during prolonged oxidation,mitigating adverse effects from bubble formation and crystallization.Due to the nanoporous structure,the oxidation rate is initially controlled by gas diffusion following a linear law before transitioning to oxide layer diffusion characterized by a parabolic law.Finally,due to different valence bond configurations,Si-C-N transforms into an amorphous SiCNO structure after phase separation,unlike the nucleation and growth of residual B-N-C.