Sublayer design and ablation resistance of CVD-TaC alternate coatings with different crystallite morphologies for C/C composites

Tantalum carbon(TaC)alternate coatings with sublayers comprised of different crystallite morphologies were prepared on carbon/carbon composites by chemical vapor deposition.Their ablative behaviors and defending mechanisms were both investigated.The specimen with the sublayer composed of columnar crystals exhibited a better ablation resistance due to the toughness enhancement induced by the lami-nated structure.However,the mechanical denudation of the sample only containing acicular crystals and the coating spallation caused by superfluous gaseous products of the sample with the sublayer composed of nanocrystals both indicate their inferior anti-ablation properties.It is believed that the results will be helpful for the structural design and practical application of chemical vapor deposition(CVD)alternate coatings.

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 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.