Deposition kinetics and mechanism of pyrocarbon for electromagnetic-coupling chemical vapor infiltration process

doi:10.1016/j.jmst.2021.06.020

Abstract

Abstract:

Although the electromagnetic-coupling chemical vapor infiltration (E-CVI) has been proven of a high-efficiency technique for producing carbon fiber reinforced pyrocarbon (PyC) matrix (C/C) composites, a deep understanding of the deposition kinetics and mechanism of PyC matrix is still lack. In this work, a deposition model with uniform electric field but gradient magnetic field was set up by using unidirectional carbon fiber bundles as the substrates to investigate the deposition kinetics and mechanism. Meanwhile, the polarizability, and the chemical adsorption and dehydrogenation barriers of hydrocarbon were simulated based on the density functional theory (DFT) and the Climb-image nudged elastic band method, respectively. The E-CVI process exhibited extremely high PyC deposition rates of 8.7, 11.5, 16.5 and 22.7 nm/s at 700, 750, 800 and 850 °C, respectively, together with a significantly low apparent activation energy of 57.9 kJ/mol within the first 5 min. The PyC deposited at different temperatures with different time shows a smooth laminar structure with low coherent length and graphitization degree. The theoretical calculation and simulation results indicated that the electrons existing on the carbon fibers and the accelerated motion of radicals with preferred orientation forced by the derived magnetic field have reduced the energy barrier for the deposition process, thereby resulting in low apparent activation energy and high PyC deposition rate. The results of this work may shed a light on how to better direct the preparation of C/C composites by E-CVI process with high quality and efficiency.

Key words: Electromagnetic-coupling chemical vapor infiltration, CVI, C/C composites, Deposition mechanism

Chenglong Hu, Rida Zhao, Sajjad Ali, Yuanhong Wang, Shengyang Pang, Jian Li, Sufang Tang. Deposition kinetics and mechanism of pyrocarbon for electromagnetic-coupling chemical vapor infiltration process[J]. J. Mater. Sci. Technol., 2022, 101: 118-127.

Figures/Tables 9

Fig. 1. Schematic diagram of the reactor and deposition process for E-CVI technique.

Fig. 2. Typical morphologies of PyC deposited by E-CVI observed by (a) PLM and (b) SEM.

Fig. 3. (a) Bright-field TEM image of fiber-PyC interface, (b) HRTEM images of PyC matrix, electron diffraction patterns of (c) fiber and (d) PyC matrix.

Fig. 4. Deposition rates of PyC vs. time curves at different temperatures.

Fig. 5. A brief summary of some reported deposition rates of PyC produced by CVI and CVD techniques [5,15,[36], [37], [38], [39], [40], [41]]

Fig. 6. (a) Deposition rates of PyC as a function of temperature at different deposition time and (b) Arrhenius plots for the deposition rate at different deposition time.

Fig. 7. A brief summary of some reported activation energies for PyC deposition process from different carbon sources [1,10,15,[42], [43], [44], [45], [46], [47], [48]]

Fig. 8. Deposition acceleration of propane and derivative radicals under the EM field (a) The calculated permanent electric dipole size D and electro-magnetic field accelerated deposition of propane and derivative radicals including chain and ring structures. (b) Zoom in plot of (a).

Fig. 9. Calculated energy barrier ∆ and current effect on dehydrogenation process of some typical molecules on top of carbon substrates (simulated as defected graphene) as a function of extra charge Q.

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