Recently,the preparation of ultra-high temperature HfC ceramic coating has gained significant attention,particularly through the application of the HfCl_(4)-CH_(4)-H_(2)-Ar system via Chemical Vapor Deposition(CVD),wh...Recently,the preparation of ultra-high temperature HfC ceramic coating has gained significant attention,particularly through the application of the HfCl_(4)-CH_(4)-H_(2)-Ar system via Chemical Vapor Deposition(CVD),which has been found widely applied to C/C composites.Herein,an analysis of the reactions that occur in the initial stage of the CVD-HfC coating process is presented using Density Functional Theory(DFT)and Transition State Theory(TST)at the B3LYP/Lanl2DZ level.The results reveal that HfCl4 can only cleave to produce hypochlorite,which will further react with methyl to synthesize intermediates to form HfC.According to the analysis of the energy barrier and reaction constant,HfCl preferentially reacts with methyl groups to form complex adsorptive intermediates at 1573 K.With a C—Hf bond production energy of 212.8 kcal/mol(1 kcal=4.18 kJ),the reaction rate constant of HfCl+CH is calculated to be 2.15×10^(-18) cm^(3)/s at 1573 K.Additionally,both the simulation and experimental results exhibit that the upward trend of reaction rate constants with temperature is also consistent with the deposition rate,indicating that the growth curve of the reaction rate constants tends to flatten out.The proposed reaction model of the precursor’s decomposition and reconstruction during deposition process has significant implication for the process guidance.展开更多
Ultra-high-temperature ceramic nanowires have shown increasing potential for use as thermal structural components.Herein,novel single-crystal Hf_(0.5)Ta_(0.5)C solid solution nanowires were synthesized and incorporate...Ultra-high-temperature ceramic nanowires have shown increasing potential for use as thermal structural components.Herein,novel single-crystal Hf_(0.5)Ta_(0.5)C solid solution nanowires were synthesized and incorporated with a HfC coating to construct a robust structure with Hf_(0.5)Ta_(0.5)C solid solution nanowires uniformly distributed and interconnected within the coating.The novel Hf_(0.5)Ta_(0.5)C solid solution nanowires could effectively hinder crack propagation through crack tip pinning and crack deflection.This mechanism substantially enhanced the elastic modulus and fracture toughness of the HfC coating by 53.29%and 59.67%,respectively.The toughened HfC coating displayed superior fracture toughness and good interfacial binding strength with the substrate to resist severe oxidation and scouring.Additionally,the high thermal conductivity of the toughened HfC coating promoted heat transmission.Thus,in comparison to the pure HfC coating,the toughened HfC coating displayed smaller mass and linear ablation rates of−0.35 mg·s^(−1)and−0.46μm·s^(−1),which decreased by 39.66%and 36.98%,respectively.Our work not only simultaneously enhances the mechanical properties and ablation resistance of HfC-coated carbon/carbon(C/C)composites but also provides novel prospects for advanced ultrahigh-temperature ceramic nanowires under extreme conditions.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 52293373 and 52130205)the National Key Research and Development Program of China (No. 2021YFA0715803)ND Basic Research Funds of Northwestern Polytechnical University, China (No. G2022WD)
文摘Recently,the preparation of ultra-high temperature HfC ceramic coating has gained significant attention,particularly through the application of the HfCl_(4)-CH_(4)-H_(2)-Ar system via Chemical Vapor Deposition(CVD),which has been found widely applied to C/C composites.Herein,an analysis of the reactions that occur in the initial stage of the CVD-HfC coating process is presented using Density Functional Theory(DFT)and Transition State Theory(TST)at the B3LYP/Lanl2DZ level.The results reveal that HfCl4 can only cleave to produce hypochlorite,which will further react with methyl to synthesize intermediates to form HfC.According to the analysis of the energy barrier and reaction constant,HfCl preferentially reacts with methyl groups to form complex adsorptive intermediates at 1573 K.With a C—Hf bond production energy of 212.8 kcal/mol(1 kcal=4.18 kJ),the reaction rate constant of HfCl+CH is calculated to be 2.15×10^(-18) cm^(3)/s at 1573 K.Additionally,both the simulation and experimental results exhibit that the upward trend of reaction rate constants with temperature is also consistent with the deposition rate,indicating that the growth curve of the reaction rate constants tends to flatten out.The proposed reaction model of the precursor’s decomposition and reconstruction during deposition process has significant implication for the process guidance.
基金the National Key R&D Program of China(No.2021YFA0715803)the National Natural Science Foundation of China(Nos.52293373 and 52130205)+1 种基金the Joint Fund of Henan Province Science and Technology R&D Program(No.225200810002)the Fundamental Research Funds of Henan Academy of Sciences(No.240621040).
文摘Ultra-high-temperature ceramic nanowires have shown increasing potential for use as thermal structural components.Herein,novel single-crystal Hf_(0.5)Ta_(0.5)C solid solution nanowires were synthesized and incorporated with a HfC coating to construct a robust structure with Hf_(0.5)Ta_(0.5)C solid solution nanowires uniformly distributed and interconnected within the coating.The novel Hf_(0.5)Ta_(0.5)C solid solution nanowires could effectively hinder crack propagation through crack tip pinning and crack deflection.This mechanism substantially enhanced the elastic modulus and fracture toughness of the HfC coating by 53.29%and 59.67%,respectively.The toughened HfC coating displayed superior fracture toughness and good interfacial binding strength with the substrate to resist severe oxidation and scouring.Additionally,the high thermal conductivity of the toughened HfC coating promoted heat transmission.Thus,in comparison to the pure HfC coating,the toughened HfC coating displayed smaller mass and linear ablation rates of−0.35 mg·s^(−1)and−0.46μm·s^(−1),which decreased by 39.66%and 36.98%,respectively.Our work not only simultaneously enhances the mechanical properties and ablation resistance of HfC-coated carbon/carbon(C/C)composites but also provides novel prospects for advanced ultrahigh-temperature ceramic nanowires under extreme conditions.
