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
The multiphoton ionization dissociation of HFC 152a and HFC 134a under the irradiation of 355 nm and 266 nm was studied in this work. Their photolyzed products were analyzed by time of flight mass spectrum instrument....The multiphoton ionization dissociation of HFC 152a and HFC 134a under the irradiation of 355 nm and 266 nm was studied in this work. Their photolyzed products were analyzed by time of flight mass spectrum instrument. The photolyzed products of HFC 152a include H +( m/z =1), C +( m/z =12), CH + 3( m/z =15), C + 2( m/z =24), CF 2H +( m/z =51), and CF +( m/z =31), whereas there is no clear products for HFC 134a photolyzation. Further, the application prospects of HFC 152a and HFC 134a in refrigeration sector were also evaluated from the view point of environmental protection, synthesis conditions and usage performance. It is suggested that HFC 152a is a better alternative compared to HFC 134a in refrigeration sector.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.
文摘The multiphoton ionization dissociation of HFC 152a and HFC 134a under the irradiation of 355 nm and 266 nm was studied in this work. Their photolyzed products were analyzed by time of flight mass spectrum instrument. The photolyzed products of HFC 152a include H +( m/z =1), C +( m/z =12), CH + 3( m/z =15), C + 2( m/z =24), CF 2H +( m/z =51), and CF +( m/z =31), whereas there is no clear products for HFC 134a photolyzation. Further, the application prospects of HFC 152a and HFC 134a in refrigeration sector were also evaluated from the view point of environmental protection, synthesis conditions and usage performance. It is suggested that HFC 152a is a better alternative compared to HFC 134a in refrigeration sector.
