Multicomponent boron-containing carbide coatings(i.e.,(Zr,Ti)C_(x)B_(y))on a C/C composite show good ablation resistance.However,the high-temperature oxidation behavior of this new type of boron-containing(Zr,Ti)C_(x)...Multicomponent boron-containing carbide coatings(i.e.,(Zr,Ti)C_(x)B_(y))on a C/C composite show good ablation resistance.However,the high-temperature oxidation behavior of this new type of boron-containing(Zr,Ti)C_(x)B_(y)solid solution ceramics has not been clarified yet.The present work fabricated(Zr,Ti)C_(x)B_(y)solid solution block ceramics by spark plasma sintering,and their oxidation behavior at 1600℃in air(N2–20-vol%O2)was investigated for the first time.The effects of boron on the oxidation resistance of(Zr,Ti)C_(x)B_(y)ceramics were examined.The results indicate that the(Zr,Ti)C_(x)B_(y)ceramics display good oxidation resistance with the parabolic rate law describing the oxidation process.After the trace solution of boron(0.5 wt%)into(Zr,Ti)Cx,the oxidation resistance of carbide ceramics is significantly enhanced,leading to a decrease of 30%in the oxidation rate constant.The formed oxide scale in the(Zr,Ti)C_(x)B_(y)ceramics is dense,and the interlayer shows stronger ability to inhibit inward diffusion of oxygen.In addition,the introduction of boron leads to more negative binding energy of(Zr,Ti)C_(x)B_(y)and improves the oxidation resistance of carbides.展开更多
Multicomponent ultra-high temperature ceramics(UHTCs)are promising candidates for thermal protection materials(TPMs)used in aerospace field.However,finding out desirable compositions from an enormous number of possibl...Multicomponent ultra-high temperature ceramics(UHTCs)are promising candidates for thermal protection materials(TPMs)used in aerospace field.However,finding out desirable compositions from an enormous number of possible compositions remains challenging.Here,through elucidating the role of preferential oxidation in ablation behavior of multicomponent UHTCs via the thermodynamic analysis and experimental verification,the correlation between the composition and ablation performance of multicomponent UHTCs was revealed from the aspect of thermodynamics.We found that the metal components in UHTCs can be thermodynamically divided into preferentially oxidized component(denoted as MP),which builds up a skeleton in oxide layer,and laggingly oxidized component(denoted as ML),which fills the oxide skeleton.Meanwhile,a thermodynamically driven gradient in the concentration of MP and ML forms in the oxide layer.Based on these findings,a strategy for pre-evaluating the ablation performance of multicomponent UHTCs was developed,which provides a preliminary basis for the composition design of multicomponent UHTCs.展开更多
Multi-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles.However,for group IV transition-metal carbides...Multi-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles.However,for group IV transition-metal carbides,the oxidation behavior of multi-component non-stoichiometric(Zr,Hf,Ti)C_(x)carbide solid solution has not been clarified yet.The present work fabricated four kinds of(Zr,Hf,Ti)C_(x)carbide solid solution powders by free-pressureless spark plasma sintering to investigate the oxidation behavior of(Zr,Hf,Ti)C_(x)in air.The effects of metallic atom composition on oxidation resistance were examined.The results indicate that the oxidation kinetics of(Zr,Hf,Ti)C_(x)are composition dependent.A high Hf content in(Zr,Hf,Ti)C_(x)was beneficial to form an amorphous Zr-Hf-Ti-C-0 oxycarbide layer as an oxygen barrier to enhance the initial oxidation resistance.Meanwhile,an equiatomic ratio of metallic atoms reduced the growth rate of(Zr,Hf,Ti)O_(2)oxide,increasing its phase stability at high temperatures,which improved the oxidation activation energy of(Zr,Hf,Ti)C_(x).展开更多
基金supported by the National Natural Science Foundation of China(No.5207021797)the Scientific Research and Technology Development Project of China National Petroleum Corporation Limited(No.2020E-2804(JT)).
文摘Multicomponent boron-containing carbide coatings(i.e.,(Zr,Ti)C_(x)B_(y))on a C/C composite show good ablation resistance.However,the high-temperature oxidation behavior of this new type of boron-containing(Zr,Ti)C_(x)B_(y)solid solution ceramics has not been clarified yet.The present work fabricated(Zr,Ti)C_(x)B_(y)solid solution block ceramics by spark plasma sintering,and their oxidation behavior at 1600℃in air(N2–20-vol%O2)was investigated for the first time.The effects of boron on the oxidation resistance of(Zr,Ti)C_(x)B_(y)ceramics were examined.The results indicate that the(Zr,Ti)C_(x)B_(y)ceramics display good oxidation resistance with the parabolic rate law describing the oxidation process.After the trace solution of boron(0.5 wt%)into(Zr,Ti)Cx,the oxidation resistance of carbide ceramics is significantly enhanced,leading to a decrease of 30%in the oxidation rate constant.The formed oxide scale in the(Zr,Ti)C_(x)B_(y)ceramics is dense,and the interlayer shows stronger ability to inhibit inward diffusion of oxygen.In addition,the introduction of boron leads to more negative binding energy of(Zr,Ti)C_(x)B_(y)and improves the oxidation resistance of carbides.
基金supported by the National Natural Science Foundation of China(52072410 and 51602349)Innovation-driven Project of Central South University.
文摘Multicomponent ultra-high temperature ceramics(UHTCs)are promising candidates for thermal protection materials(TPMs)used in aerospace field.However,finding out desirable compositions from an enormous number of possible compositions remains challenging.Here,through elucidating the role of preferential oxidation in ablation behavior of multicomponent UHTCs via the thermodynamic analysis and experimental verification,the correlation between the composition and ablation performance of multicomponent UHTCs was revealed from the aspect of thermodynamics.We found that the metal components in UHTCs can be thermodynamically divided into preferentially oxidized component(denoted as MP),which builds up a skeleton in oxide layer,and laggingly oxidized component(denoted as ML),which fills the oxide skeleton.Meanwhile,a thermodynamically driven gradient in the concentration of MP and ML forms in the oxide layer.Based on these findings,a strategy for pre-evaluating the ablation performance of multicomponent UHTCs was developed,which provides a preliminary basis for the composition design of multicomponent UHTCs.
基金supported by the National Natural Science Foundation of China(Nos.51602349 and 5207021797)the Fundamental Research Funds for the Central Universities,the Key Research and Development(R&D)Program in Hunan Province Science and Technology Department(No.2018GK2061)the Innovation-drive Project of Central South University.
文摘Multi-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles.However,for group IV transition-metal carbides,the oxidation behavior of multi-component non-stoichiometric(Zr,Hf,Ti)C_(x)carbide solid solution has not been clarified yet.The present work fabricated four kinds of(Zr,Hf,Ti)C_(x)carbide solid solution powders by free-pressureless spark plasma sintering to investigate the oxidation behavior of(Zr,Hf,Ti)C_(x)in air.The effects of metallic atom composition on oxidation resistance were examined.The results indicate that the oxidation kinetics of(Zr,Hf,Ti)C_(x)are composition dependent.A high Hf content in(Zr,Hf,Ti)C_(x)was beneficial to form an amorphous Zr-Hf-Ti-C-0 oxycarbide layer as an oxygen barrier to enhance the initial oxidation resistance.Meanwhile,an equiatomic ratio of metallic atoms reduced the growth rate of(Zr,Hf,Ti)O_(2)oxide,increasing its phase stability at high temperatures,which improved the oxidation activation energy of(Zr,Hf,Ti)C_(x).
