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

Recently, the preparation of ultra-high temperature HfC ceramic coating has gained significant attention, particularly through the application of the HfCl₄-CH₄-H₂-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 cm³/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.