Hexagonal boron nitride(h-BN)ceramics have become exceptional materials for heat-resistant components in hypersonic vehicles,owing to their superior thermal stability and excellent dielectric properties.However,their ...Hexagonal boron nitride(h-BN)ceramics have become exceptional materials for heat-resistant components in hypersonic vehicles,owing to their superior thermal stability and excellent dielectric properties.However,their densification during sintering still poses challenges for researchers,and their mechanical properties are rather unsatisfactory.In this study,SrAl_(2)Si_(2)O_(8)(SAS),with low melting point and high strength,was introduced into the h-BN ceramics to facilitate the sintering and reinforce the strength and toughness.Then,BN-SAS ceramic composites were fabricated via hot press sintering using h-BN,SrCO_(3),Al_(2)O_(3),and SiO_(2) as raw materials,and effects of sintering pressure on their microstructure,mechanical property,and thermal property were investigated.The thermal shock resistance of BN-SAS ceramic composites was evaluated.Results show that phases of as-preparedBN-SAS ceramic composites are h-BN and h-SrAl_(2)Si_(2)O_(8).With the increase of sintering pressure,the composites’densities increase,and the mechanical properties shew a rising trend followed by a slight decline.At a sintering pressure of 20 MPa,their bending strength and fracture toughness are(138±4)MPa and(1.84±0.05)MPa·m^(1/2),respectively.Composites sintered at 10 MPa exhibit a low coefficient of thermal expansion,with an average of 2.96×10^(-6) K^(-1) in the temperature range from 200 to 1200℃.The BN-SAS ceramic composites prepared at 20 MPa display higher thermal conductivity from 12.42 to 28.42 W·m^(-1)·K^(-1) within the temperature range from room temperature to 1000℃.Notably,BN-SAS composites exhibit remarkable thermal shock resistance,with residual bending strength peaking and subsequently declining sharply under a thermal shock temperature difference ranging from 600 to 1400℃.The maximum residual bending strength is recorded at a temperature difference of 800℃,with a residual strength retention rate of 101%.As the thermal shock temperature difference increase,the degree of oxidation on the ceramic surface and cracks due to thermal stress are also increased gradually.展开更多
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...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.展开更多
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 circumvent...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.展开更多
基金National Natural Science Foundation of China (52072088, 52072089)Natural Science Foundation of Heilongjiang Province (LH2023E061)+1 种基金Scientific and Technological Innovation Leading Talent of Harbin Manufacturing (2022CXRCCG001)Fundamental Research Funds for the Central Universities (3072023CFJ1003)。
文摘Hexagonal boron nitride(h-BN)ceramics have become exceptional materials for heat-resistant components in hypersonic vehicles,owing to their superior thermal stability and excellent dielectric properties.However,their densification during sintering still poses challenges for researchers,and their mechanical properties are rather unsatisfactory.In this study,SrAl_(2)Si_(2)O_(8)(SAS),with low melting point and high strength,was introduced into the h-BN ceramics to facilitate the sintering and reinforce the strength and toughness.Then,BN-SAS ceramic composites were fabricated via hot press sintering using h-BN,SrCO_(3),Al_(2)O_(3),and SiO_(2) as raw materials,and effects of sintering pressure on their microstructure,mechanical property,and thermal property were investigated.The thermal shock resistance of BN-SAS ceramic composites was evaluated.Results show that phases of as-preparedBN-SAS ceramic composites are h-BN and h-SrAl_(2)Si_(2)O_(8).With the increase of sintering pressure,the composites’densities increase,and the mechanical properties shew a rising trend followed by a slight decline.At a sintering pressure of 20 MPa,their bending strength and fracture toughness are(138±4)MPa and(1.84±0.05)MPa·m^(1/2),respectively.Composites sintered at 10 MPa exhibit a low coefficient of thermal expansion,with an average of 2.96×10^(-6) K^(-1) in the temperature range from 200 to 1200℃.The BN-SAS ceramic composites prepared at 20 MPa display higher thermal conductivity from 12.42 to 28.42 W·m^(-1)·K^(-1) within the temperature range from room temperature to 1000℃.Notably,BN-SAS composites exhibit remarkable thermal shock resistance,with residual bending strength peaking and subsequently declining sharply under a thermal shock temperature difference ranging from 600 to 1400℃.The maximum residual bending strength is recorded at a temperature difference of 800℃,with a residual strength retention rate of 101%.As the thermal shock temperature difference increase,the degree of oxidation on the ceramic surface and cracks due to thermal stress are also increased gradually.
基金the National Natural Science Foundation of China(Nos.52372059,52172068,52232004,and 52002092)the Heilongjiang Natural Science Fund for Young Scholars(No.YQ2021E017)+3 种基金the Fundamental Research Funds for the Central Universities(No.2022FRFK060012)the Heilongjiang Touyan Team Program,and the Advanced Talents Scientific Research Foundation of Shenzhen:Yu Zhou.the Beijing Engineering Research Center of Efficient and Green Aerospace Propulsion Technology and Advanced Space Propulsion Laboratory of BICE(No.LabASP-2023-11)the Huiyan Action(No.1A423653)the Key Technologies R&D Program of CNBM(No.2023SJYL05).Ralf Riedel also gratefully acknowledges the financial support provided by the Research Training Group 2561“MatCom-ComMat:Materials Compounds from Composite Materials for Applications in Extreme Conditions”funded by the Deutsche Forschungsgemeinschaft(DFG),Bonn,Germany.
文摘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.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.52372059,52172068,52232004,and 52002092)the Heilong Jiang Natural Science Fund for Young Scholars(No.YQ2021E017)+2 种基金the Fundamental Research Funds for the Central Universities(No.2022FRFK060012)the Heilongjiang Touyan Team Program,and the Advanced Talents Scientific Research Foundation of Shenzhen:Yu ZhouThis work was also funded by the Beijing Engineering Research Center of Efficient and Green Aerospace PropulsionTechnology and Advanced Space Propulsion Laboratory of Beijing Institute of Control Engineering(BICE)(No.LabASP-2023-11).
文摘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.