Initial precursor reaction mechanism of CVD-HfC coating based on density functional theory  

作　　者：Yunzhou LIN Yulei ZHANG Yanqin FU Jian ZHANG Jing’an KONG Ruicong CHEN 

机构地区：[1]State Key Laboratory of Solidification Processing,Carbon/Carbon Composites Research Center,Northwestern Polytechnical University,Xi’an 710072,China [2]Henan Key Laboratory of High Performance Carbon Fiber Reinforced Composites,Carbon Matrix Composites Research Institute,Henan Academy of Sciences,Zhengzhou 450046,China

出　　处：《Chinese Journal of Aeronautics》2024年第7期511-521,共11页中国航空学报（英文版）

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)

摘　　要：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.

关 键 词：Carbon composite HfC coating Chemical vapor deposition Density functional theory Precursor reaction mechanism 

分 类 号：V25[一般工业技术—材料科学与工程] TB306[航空宇航科学与技术—航空宇航制造工程]