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
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 a...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).展开更多
Conventional boron nitride(BN)-based composites are often limited by high porosity and long processing cycles,which severely restrict their mechanical performance and engineering applications.To overcome these limitat...Conventional boron nitride(BN)-based composites are often limited by high porosity and long processing cycles,which severely restrict their mechanical performance and engineering applications.To overcome these limitations,a novel organic-inorganic hybrid matrix combined with a hot-compression orientation strategy is proposed.Liquid-phase polyborazylene(PBZ)was employed to promote the rearrangement and alignment of h-BN lamellae during pressing,and subsequent pyrolysis yielded a dense and continuous BN matrix with in situ precipitated nanocrystals serving as loadtransfer nodes.This process significantly enhanced densification,reduced porosity,and enabled the construction of an ordered lamellar structure.Unlike conventional PIP processes that typically require~10 repeated infiltration-pyrolysis cycles,this method achieves dense composites in a single pyrolysis step,effectively avoiding fiber damage and greatly shortening the fabrication cycle.The synergistic effects of aligned lamellae inducing extended crack propagation paths and in situ nanocrystals providing additional load-transfer mechanisms effectively improved the mechanical performance of the composites.The proposed PBZ-assisted hybrid matrix and lamellar-orientation design strategy offers a new and efficient route for developing high-performance BN-based composites with excellent wave-transmitting and thermal protection capabilities.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financially supported by the National Natural Science Foundation of China(Grant no.52002092,51832002,52172068,52232004,52372059)Heilong Jiang Natural Science Fund for Young Scholars(Grant no.YQ2021E017)+2 种基金National Key Research and Development Program of China(Grant no.2017YFB0310400)Heilongjiang Touyan Team Program,Advanced Talents Scientific Research Foundation of Shenzhen,and Fundamental Research Funds for the Central Universities(2022FRFK0600XX)RR 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).
基金supported by the National Key Research and Development Program of China(No.2024YFB3714702)the National Natural Science Foundation of China(Nos.52072088 and 52072089)+1 种基金the Natural Science Foundation of Heilongjiang Province(No.LH2023E061)the Scientific and Technological Innovation Leading Talent of Harbin Manufacturing(No.2022CXRCCG001).
文摘Conventional boron nitride(BN)-based composites are often limited by high porosity and long processing cycles,which severely restrict their mechanical performance and engineering applications.To overcome these limitations,a novel organic-inorganic hybrid matrix combined with a hot-compression orientation strategy is proposed.Liquid-phase polyborazylene(PBZ)was employed to promote the rearrangement and alignment of h-BN lamellae during pressing,and subsequent pyrolysis yielded a dense and continuous BN matrix with in situ precipitated nanocrystals serving as loadtransfer nodes.This process significantly enhanced densification,reduced porosity,and enabled the construction of an ordered lamellar structure.Unlike conventional PIP processes that typically require~10 repeated infiltration-pyrolysis cycles,this method achieves dense composites in a single pyrolysis step,effectively avoiding fiber damage and greatly shortening the fabrication cycle.The synergistic effects of aligned lamellae inducing extended crack propagation paths and in situ nanocrystals providing additional load-transfer mechanisms effectively improved the mechanical performance of the composites.The proposed PBZ-assisted hybrid matrix and lamellar-orientation design strategy offers a new and efficient route for developing high-performance BN-based composites with excellent wave-transmitting and thermal protection capabilities.
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.
