Ti-doped Hf(Zr)B2-SiC Anti-ablation Coatings: Preparation and Ablation Resistance Mechanism

doi:10.15541/jim20240249

Abstract

Abstract:

In order to improve the ablation resistance of carbon-based materials in elevated-temperature and oxygenated environments, Ti-doped HfB₂-SiC and ZrB₂-SiC composite coatings were prepared on the surface of graphite via a hybrid method involving slurry dipping and reactive infiltration. Phase compositions, microstructures, and element distributions of the composite coatings were studied, and anti-ablation ability of the coating was evaluated at 2300 ℃. Results show that structures of Ti-doped Hf(Zr)B₂-SiC composite coatings are very dense after silicon infiltration. Both HfTiB₂ and ZrTiB₂ ceramic phases are embedded in the coatings, which exhibit no defects and establish robust bonds with the graphite substrates. Residual silicon continuously distributes around Hf(Zr)B₂ and SiC particles. After undergoing ablation at 2300 ℃ for 480 s, the mass ablation rates of HfTiB₂-SiC and ZrTiB₂-SiC composite coating samples are -2.71×10^-3 and -4.20×10^-1 mg/s, respectively, indicating a slight weight gain. The corresponding line ablation rates are 1.88×10^-4 and 3.70×10^-4 μm/s, respectively. Following ablation, a Hf-Ti-Si-O multiphase oxide layer composed of HfTiO₄-HfO₂ as the skeleton and TiO₂-SiO₂ as the filling phase forms on the surface of HfTiB₂-SiC coating. In contrast, a Zr-Ti-Si-O multiphase oxide layer with some micropores, comprising embedded ZrTiO₄ and ZrO₂ phases and a semi-continuous SiO₂ glass phase, develops on the ablative surface of ZrTiB₂-SiC coating. High-melting-point phases, such as HfTiO₄, HfO₂, ZrTiO₄, and ZrO₂, effectively counteract high-temperature flame erosion. Meanwhile, TiO₂ and SiO₂, possessing high-temperature fluidity, can seal the pore defects generated by erosion and thereby preventing oxygen from diffusing into the coatings and substrates. Therefore, the synergy between high-temperature skeletons and filling phases significantly enhances the anti-ablation protection of coatings.

Key words: ceramic coating, ablation resistance, slurry dipping, reaction infiltration, multiphase glass layer

CLC Number:

TQ174

GUO Xiaoyang, ZHANG Xiaolin, JIANG Yan, TIAN Yuan, GENG Zhi. Ti-doped Hf(Zr)B₂-SiC Anti-ablation Coatings: Preparation and Ablation Resistance Mechanism[J]. Journal of Inorganic Materials, 2024, 39(12): 1357-1366.

Figures/Tables 14

Fig. 1 Preparation process of the coating sample

Fig. 2 XRD pattern, surface and cross-sectional microstructures, and EDS element analysis of HfTiB2-SiC coating (a) XRD pattern; (b) Surface morphology; (c) Enlarged view of Fig. (b); (d) EDS element mappings of Fig. (c); (e) EDS element point-analysis of Fig. (c); (f) Cross-sectional morphology; (g) Enlarged view of Fig. (f); (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (g)

Fig. 3 XRD pattern, surface and cross-sectional microstructures, and EDS element analysis of ZrTiB2-SiC coating (a) XRD pattern; (b) Surface morphology; (c) Enlarged view of Fig. (b); (d) EDS element mappings of Fig. (c); (e) EDS element point-analysis of Fig. (c); (f) Cross-sectional morphology; (g) Enlarged view of Fig. (f); (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (g)

Fig. 4 XRD pattern, surface and cross-sectional microstructures, and element distribution of HfTiB2-SiC coating sample after ablation for 480 s (a) XRD pattern; (b) Surface microscopic morphology of the ablation center; (c) Enlarged view of Fig. (b); (d) EDS element mappings of Fig. (c); (e) Microscopic morphology of the transition zone; (f) Surface element analysis of Fig. (e); (g) Cross-sectional morphology of the ablation center; (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (c, g)

Fig. 5 XRD pattern, microstructures and element distributions of the ablation center surface and cross-sectional of ZrTiB2-SiC coating sample after ablation for 480 s (a) XRD pattern; (b) Surface microstructure; (c) Enlarged view of Fig. (b); (d) Enlarged view of Fig. (c); (e) EDS element mappings of Fig. (d); (f) Cross-sectional microscopic morphology; (g) Enlarged view of Fig. (f); (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (d, g)

Fig. 6 Gibbs free energy variation curves with temperature for the reaction occurring during coating ablation process

Fig. 7 Temperature dependent curves of vapor pressure (a) and decomposition pressure (b) for the oxidation products during coating ablation process

Fig. 8 Schematic diagram of composite coating ablation process (a) Before ablation; (b) During ablation; (c) After ablation

Fig. S1 XRD pattern, surface and cross-sectional microstructures and EDS element analysis of HfTiB2-SiC coating after plasma flame ablation for 150 s (a) XRD pattern; (b) Surface microstructure; (c) Enlarged view of Fig. (b); (d) Enlarged view of the ablation center; (e) Surface element analysis of Fig. (d); (f) Cross-sectional morphology; (g) Enlarged view of Fig. (f); (h) Surface element analysis of Fig. (g); (i) Element point analysis of Fig. (d, g)

Table S1 Element atomic fraction of Spot 1 in Fig. 2(c)

Element	Spot 1/%
B	30.42
C	59.20
Si	0.66
Ti	2.00
Hf	7.72

Table S2 Element atomic fraction of Spot 1 in Fig. 3(c)

Element	Spot 1/%
B	57.66
C	30.13
Si	0
Ti	2.87
Zr	9.35

Table S3 Eelement atomic fraction of Spots 1-3 in Fig. 4(c)

Element	Spot 1/%	Spot 2/%	Spot 3/%
O	64.15	64.42	60.46
Si	3.70	33.04	16.30
Ti	0.24	0.55	0.37
Hf	31.91	1.99	22.87

Table S4 Element atomic fraction of Spots 1-3 in Fig. 5(d)

Element	Spot 1/%	Spot 2/%	Spot 3/%
O	64.20	72.86	57.10
Si	1.75	13.14	29.01
Ti	2.69	2.56	5.31
Zr	31.36	11.44	8.58

Table S5 Element atomic fraction of Spots 4 and 6 in Fig. 5(g)

Element	Spot 4/%	Spot 6/%
C	17.38	12.51
O	42.38	59.93
Si	0.59	20.94
Ti	2.38	4.75
Zr	37.27	1.86

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Ti-doped Hf(Zr)B₂-SiC Anti-ablation Coatings: Preparation and Ablation Resistance Mechanism

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