Laser-Plasma Deposition of Silicon Carbonitride Films by the HMDS Vapor Gas Flow Activation after a Laser Beam Focus

A new laser-plasma deposition method has been developed for the plasma chemical deposition of hard silicon carbonitride coatings on stainless steel substrates from the hexamethyldisilazane (HMDS) Si2NH(CH3)6 vapor in a high-speed Ar and Ar + 10 vol.% He gas stream at the HMDS gas flow activation after the laser beam focus. The method allows depositing silicon carbonitride coatings at the rate of 0.4 - 1.2 μm·min-1, i.e. ~2 times higher than that at introducing HMDS in the laser beam focus zone. The properties of the prepared coatings have been studied by the methods of IR and Raman spectroscopy, atomic force microscopy, nanoindentation and X-ray diffraction (XRD) analysis. Studying the film structure with the use of XRD showed that the prepared silicon carbonitride coatings are X-ray amorphous. It has been found that the coating deposition rate and the structure of coatings depend on the process parameters: HMDS flow rate and plasma-generating gas (argon or (Ar + He). The method allows depositing SiCN films at a high speed and a hardness of 20 - 22 GPa.

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.

Fabrication of electrical semi-conductive SiCN ceramics by vat photopolymerization

The emergence of additive manufacturing(AM)enables ceramics to be fabricated with customized geometry,and polymer-derived ceramics(PDCs)has attracted growing attention owing to their irreplaceable advantages.The combination of 3D printing and PDCs endows the resultant ceramics with both precision and performance.However,AM of ceramics from preceramic polymers is still challenging,and insufficient investigation of functionality also limits the versatility of precursor and its derived ceramics.Herein,we propose a novel paradigm for 3D printing dense silicon carbonitride ceramic and study its electrical semiconducting properties.The formulated photosensitive precursor inks could achieve self-polymerization and cross-linking under the radiation of UV light(405 nm).The green body with intricate structures is fabricated by digital light processing(DLP).Lightweight(1.79-2.08 g cm^(-3))and low porosity(<5%)amorphous ceramics were obtained after thermal treatments.Processes of cross-linking,decomposition,and ceramization are monitored and analyzed.Furthermore,the semi-conducting behaviors of resultant ceramics are identified where the conductivity(10^(-5)-10^(-1)S m^(-1))has a monotonic correspondence with the testing temperatures(25-1000℃).The numerical relationship is fitted by exponential functions,and its conducting mechanism could be interpreted by the band tail hopping(BTH)model.This work could provide alternative solutions for the fabrication of PDCs and potentials for sensing applications.

Formation of nanocrystalline graphite in polymer-derived SiCN by polymer infiltration and pyrolysis at a low temperature

The microstructure of polymer-derived ceramics(PDCs)was closely related to processing.This study demonstrated that SiCN matrix prepared by polymer infiltration and pyrolysis(PIP)at 900℃ inside a Si_(3)N_(4) whisker(Si_(3)N_(4w))preform with submicro-sized pores differed from its powder-consolidated analogue in both the content and structure of free carbon.Chemical analysis showed that PIP process had a higher free carbon yield.Raman spectroscopy and transmission electron microscopy(TEM)observation discovered a higher graphitization degree of free carbon and the existence of nanocrystalline graphite in SiCN matrix.Dielectric properties of Si_(3)N_(4w)/SiCN composites were greatly enhanced when volume fraction of SiCN matrix reached 24.5%due to dielectric percolation caused by highly-lossy free carbon.Reconsolidation of hydrocarbon released during pyrolysis by gas-state carbonization in Si_(3)N_(4) whisker preform was supposed to account for the high yield and graphitization degree of free carbon in PIP process.