Oxidation behavior of amorphous and nanocrystalline SiBCN ceramics–Kinetic consideration and microstructure

In this study,the structural evolution of SiBCN ceramics during crystallization and its effects on oxidation behavior involving different atomic units or formed phases in amorphous or crystalline SiBCN ceramics were analyzed.The amorphous structure has exceptionally high oxidation activity but presents much better oxidation resistance due to its synchronous oxidation of atomic units and homogeneous composition in the generated oxide layer.However,the oxidation resistance of SiBCN ceramic will degrade during the continual crystallization process,especially for the formation of the nanocapsule-like structure,due to heterogeneous oxidation caused by the phase separation.Besides,the activation energy and rate-controlling mechanism of the atomic units and phases in SiBCN ceramics were obtained.The BNCx(Ea=145 kJ/mol)and SiC(2-x)(Ea=364 kJ/mol)atomic units in amorphous SiBCN structure can be oxidized at relatively lower temperatures with much lower activation energy than the corresponding BN(C)(Ea=209 kJ/mol)and SiC(Ea=533 kJ/mol)phases in crystalline structure,and the synchronous oxidation of the SiC(2-x)and BNCx units above 750C changes the oxidation activation energy of BNCx(Ea=332 kJ/mol)to that similar to SiC(2-x).The heterogeneous oxide layer formed from the nanocapsule-like structure will decrease the activation energy SiC(Ea=445 kJ/mol)and t-BN(Ea=198 kJ/mol).

Polymer-derived SiBCN ceramic pressure sensor with excellent sensing performance

Pressure measurement with excellent stability and long time durability is highly desired,especially at high temperature and harsh environments.A polymer-derived silicoboron carbonitride(SiBCN)ceramic pressure sensor with excellent stability,accuracy,and repeatability is designed based on the giant piezoresistivity of SiBCN ceramics.The SiBCN ceramic sensor was packaged in a stainless steel case and tested using half Wheatstone bridge with the uniaxial pressure up to 10 MPa.The SiBCN ceramic showed a remarkable piezoresistive effect with the gauge factor(K)as high as 5500.The output voltage of packed SiBCN ceramic sensor changes monotonically and smoothly versus external pressure.The as received SiBCN pressure sensor possesses features of short response time,excellent repeatability,stability,sensitivity,and accuracy.Taking the excellent high temperature thermo-mechanical properties of polymer-derived SiBCN ceramics(e.g.,high temperature stability,oxidation/corrosion resistance)into account,SiBCN ceramic sensor has significant potential for pressure measurement at high temperature and harsh environments.

Novel C_(sf)/SiBCN composites prepared by densifying C_(sf)/MA-SiBCN with the PIP process:Oxidation behavior and damage mechanism

To improve the oxidation resistance of short carbon fiber(C_(sf))-reinforced mechanically alloyed SiBCN(MA-SiBCN)(C_(sf)/MA-SiBCN)composites,dense amorphous C_(sf)/SiBCN composites containing both MA-SiBCN and polymer-derived ceramics SiBCN(PDCs-SiBCN)were prepared by repeated polymer infiltration and pyrolysis(PIP)of layered C_(sf)/MA-SiBCN composites at 1100℃,and the oxidation behavior and damage mechanism of the as-prepared C_(sf)/SiBCN at 1300–1600℃ were compared and discussed with those of C_(sf)/MA-SiBCN.The C_(sf)/MA-SiBCN composites resist oxidation attack up to 1400℃ but fail at 1500℃ due to the collapse of the porous framework,while the PIP-densified C_(sf)/SiBCN composites are resistant to static air up to 1600℃.During oxidation,oxygen diffuses through preexisting pores and the pores left by oxidation of carbon fibers and pyrolytic carbon(PyC)to the interior of the matrix.Owing to the oxidative coupling effect of the MA-SiBCN and PDCs-SiBCN matrices,a relatively continuous and dense oxide layer is formed on the sample surface,and the interfacial region between the oxide layer and the matrix of the as-prepared composite contains an amorphous glassy structure mainly consisting of Si and O and an incompletely oxidized but partially crystallized matrix,which is primarily responsible for improving the oxidation resistance.

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.