Microstructure and Ablation Resistance of C/C Composites Modified by Hf-Si-Based Coating-Matrix Integrated Structure Fabricated by Reactive Melt Infiltration

doi:10.15541/jim20250424

Abstract

Abstract: To enhance the ablation resistance of C/C composites under ultra-high-temperature and long-duration conditions, a non-embedded reactive melt infiltration technique was employed to fabricate an Hf-Si-based coating-matrix integrated modified C/C composite. Microstructural analysis revealed that the coating and matrix primarily consist of HfC, SiC, and HfSi₂, with strong interfacial bonding formed between them through chemical reactions. Within the materials, the matrix density and composition exhibited a gradient distribution along the infiltration direction. Specifically, regions proximal to the infiltration source were denser and rich in HfC-HfSi₂ phases, whereas distal regions were more porous, with the matrix consisting mainly of SiC and Si-HfSi₂ eutectic structure. The surface coating was continuous and dense, with a uniform thickness of approximately 120 µm. It featured a distinct bilayer architecture composed of an outer SiC layer and an inner HfC-HfSi₂-SiC layer. An in-depth investigation of the reaction mechanism revealed that the HfC-SiC-HfSi₂ coating-matrix integrated structure forms through a synergistic effect of melt infiltration-reaction and vapor permeation-deposition. The composite exhibited exceptional ablation resistance when exposed to an oxyacetylene flame. After ablation tests conducted at 2500 °C for 60, 180, 600, and 3540 s, the linear ablation rates were -3.52, -1.35, -0.85, and 0.118 μm/s, respectively. This outstanding performance is attributed to the in-situ formation of a dual-layer oxide barrier. A dense, continuous HfO₂ layer generated from the surface coating works in concert with a multiphase HfO₂-SiO₂-HfSiO₄ oxide layer generated from substrate oxidation. Together, these layers effectively retard inward oxygen diffusion and suppress the oxidative ablation process. This work proposes a viable strategy for designing and fabricating high-performance integrated thermal protection structures.

Key words: reactive melt infiltration, UHTCs, coating-matrix integration, microstructure, ablation resistance

CLC Number:

TB332

ZHAO Tongtong, DAI Jixiang, SU Cheng, SHI Yan, SHA Jianjun. Microstructure and Ablation Resistance of C/C Composites Modified by Hf-Si-Based Coating-Matrix Integrated Structure Fabricated by Reactive Melt Infiltration[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250424.

References

[1] ZENG Y, WANG D, XIONG X, et al. Ablation-resistant carbide Zr_0.8Ti_0.2C_0.74B_0.26 for oxidizing environments up to 3,000°C. Nature Communications, 2017, 8: 15836.
[2] SCITI D, ZOLI L, REIMER T, et al. A systematic approach for horizontal and vertical scale up of sintered ultra-high temperature ceramic matrix composites for aerospace—advances and perspectives. Composites Part B: Engineering, 2022, 234: 109709.
[3] Padture N P.Advanced structural ceramics in aerospace propulsion.Nature Materials, 2016, 15(8): 804.
[4] 陈玉峰, 洪长青, 胡成龙, 等. 空天飞行器用热防护陶瓷材料. 现代技术陶瓷, 2017, 38(05): 311.
[5] ARAI Y, INOUE R, GOTO K, et al. Carbon fiber reinforced ultra-high temperature ceramic matrix composites: a review. Ceramics International, 2019, 45(12): 14481.
[6] ZHU S, ZHANG G, BAO Y, et al. Progress in preparation and ablation resistance of ultra-high-temperature ceramics modified C/C composites for extreme environment. Reviews on Advanced Materials Science, 2023, 62(1): 20220276.
[7] NI D, CHENG Y, ZHANG[J], et al. Advances in ultra-high temperature ceramics, composites, and coatings. Journal of Advanced Ceramics, 2021, 11(1): 1.
[8] PARK S J.Carbon/Carbon Composites. In: PARK S J. Carbon Fibers. Singapore: Springer Singapore, 2018: 279.
[9] ZHANG J P, QU J L, FU Q G.Ablation behavior of nose-shaped HfB₂-SiC modified carbon/carbon composites exposed to oxyacetylene torch.Corrosion Science, 2019, 151: 87.
[10] JIN X, FAN X, LU C, et al. Advances in oxidation and ablation resistance of high and ultra-high temperature ceramics modified or coated carbon/carbon composites. Journal of the European Ceramic Society, 2018, 38(1): 1.
[11] FAHRENHOLTZ W G, HILMAS G E.Ultra-high temperature ceramics: materials for extreme environments.Scripta Materialia, 2017, 129: 94.
[12] ZHANG X H, WANG Y M, CHENG Y,et al. Research progress on ultra-high temperature ceramic composites. Journal of Inorganic Materials, 2024, 39(6): 571.
[13] WYATT B C, NEMANI S K, HILMAS G E, et al. Ultra-high temperature ceramics for extreme environments. Nature Reviews Materials, 2023, 9: 773.
[14] LI X X, FU Q G, WEN Z H,et al. Research progress on ultra-high temperature ceramic structural materials for extreme environments. Journal of Inorganic Materials, 2025, 40(10): 1045.
[15] LIU Z, WANG Y, XIONG X, et al. Microstructure and ablation behavior of C/C-SiC-(Zr_xHf₁-_x)C composites prepared by reactive melt infiltration method. Materials, 2023, 16(5): 2120.
[16] JIAO X, TAN Q, HE Q, et al. Cyclic ablation behavior of mullite-modified C/C-HfC-SiC composites under an oxyacetylene flame at about 2400 °C. Journal of the European Ceramic Society, 2023, 43(10): 4309.
[17] WANG Y L, XIONG X, ZHAO X[J], et al. Structural evolution and ablation mechanism of a hafnium carbide coating on a C/C composite in an oxyacetylene torch environment. Corrosion Science, 2012, 61: 156.
[18] CHEN Y, SUN W, XIONG X, et al. Microstructure, thermophysical properties, and ablation resistance of C/HfC-ZrC-SiC composites. Ceramics International, 2019, 45(4): 4685.
[19] VERDON C, SZWEDEK O, ALLEMAND A, et al. High temperature oxidation of two-and three-dimensional hafnium carbide and silicon carbide coatings. Journal of the European Ceramic Society, 2014, 34(4): 879.
[20] DUAN L, ZHAO X, WANG Y.Comparative ablation behaviors of C/SiC-HfC composites prepared by reactive melt infiltration and precursor infiltration and pyrolysis routes.Ceramics International, 2017, 43(18): 16114.
[21] CHEN B W, NI D W, WANG J X, et al. Ablation behavior of C_f/ZrC-SiC-based composites fabricated by an improved reactive melt infiltration. Journal of the European Ceramic Society, 2019, 39(15): 4617.
[22] LIU Z, FU Q, SHI H, et al. Comparative study of microstructure and ablation behaviour of C/C-HfC-SiC composites prepared under two different conditions. Materials Characterization, 2022, 194: 112467.
[23] ZHAO R, PANG S, LIANG B, et al. Comparative ablation behaviors of C/SiC-ZrC and C/SiC-HfC composites prepared by ceramization of carbon aerogel preforms. Corrosion Science, 2023, 225: 111623.
[24] KOU S, MAO Y, MA[J], et al. Microstructure evolution and properties of Hf/Zr-based UHTCs modified C/C composites prepared by reactive melt infiltration method. Journal of the European Ceramic Society, 2024, 44(6): 3610.
[25] YAN M, LI H, FU Q, et al. Ablative property of C/C-SiC-HfC composites prepared via precursor infiltration and pyrolysis under 3,000 °C oxyacetylene torch. Acta Metallurgica Sinica (English Letters), 2014, 27(6): 981.
[26] YAN C, LIU R, ZHA B, et al. Fabrication and properties of 3-dimensional 4-directional C_f/HfC-SiC composites by precursor impregnation and pyrolysis process. Journal of Alloys and Compounds, 2018, 739: 955.
[27] ZHANG J, XIN Y, WANG R, et al. Ablation behaviour of C/C-HfC-SiC composites prepared by joint route of precursor infiltration and pyrolysis and gaseous silicon infiltration. Chinese Journal of Aeronautics, 2023, 36(9): 426.
[28] ZHANG M, HU D, FU Q.Ablation resistant behavior of silicide modified HfB₂-SiC coating on graphite by spark plasma sintering: Role of MeSi₂ addition.Journal of the European Ceramic Society, 2024, 44(11): 6286.
[29] GIGOLOTTI J C J, NUNES C A, SUZUKI P A, et al. Evaluation of phase equilibria involving the liquid phase in the Hf-Si system. Journal of Phase Equilibria and Diffusion, 2014, 35(5): 622.
[30] ZHOU L, FU Q, HU D, et al. Oxidation protective SiC-Si coating for carbon/carbon composites by gaseous silicon infiltration and pack cementation: a comparative investigation. Journal of the European Ceramic Society, 2021, 41(1): 194.
[31] HOU J Q, CHEN R C, ZENG Y Y,et al. Thermal shock and ablation resistance of SiC coating repaired by gaseous silicon infiltration. Journal of Inorganic Materials, 2025, 40(2): 168.
[32] HAGGERTY R P, SARIN P, APOSTOLOV Z D, et al. Thermal Expansion of HfO₂ and ZrO₂. Journal of the American Ceramic Society, 2014, 97(7): 2213.
[33] WANG P, LI H, SUN[J], et al. The effect of HfB₂ content on the oxidation and thermal shock resistance of SiC coating. Surface and Coatings Technology, 2018, 339: 124.
[34] SHEN Y, SUN W, XU Y, et al. Structural characteristics and ablative behavior of YF₃ modified C/C-ZrC-SiC composites and their preparation by molten salt assisted reactive melt infiltration. Journal of the European Ceramic Society, 2023, 43(4): 1303.
[35] JIAO X, HE Q, QING M, et al. Ablation behavior of C/C-Zr₁-_xHf_xC-SiC composites under an oxyacetylene flame at above 2500 °C. Journal of Materials Research and Technology, 2023, 24: 3235.
[36] YAN C, LIU R, CAO Y, et al. Ablation behavior and mechanism of C/ZrC, C/ZrC-SiC and C/SiC composites fabricated by polymer infiltration and pyrolysis process. Corrosion Science, 2014, 86: 131.
[37] RAN L P, RAO F, PENG K, et al. Preparation and properties of C/C-ZrB₂-SiC composites by high-solid-loading slurry impregnation and polymer infiltration and pyrolysis (PIP). Transactions of Nonferrous Metals Society of China, 2019, 29(10): 2141.
[38] CHANG Y, SUN W, XIONG X, et al. Microstructure and ablation behaviors of a novel gradient C/C-ZrC-SiC composite fabricated by an improved reactive melt infiltration. Ceramics International, 2016, 42(15): 16906.
[39] XIE J, LI K, LI H, et al. Ablation behavior and mechanism of C/C-ZrC-SiC composites under an oxyacetylene torch at 3000 °C. Ceramics International, 2013, 39(4): 4171.
[40] LIU Y, FU Q, WANG B, et al. The ablation behavior and mechanical property of C/C-SiC-ZrB₂ composites fabricated by reactive melt infiltration. Ceramics International, 2017, 43(8): 6138.
[41] LI K, XIE J, LI H, et al. Ablative and mechanical properties of C/C-ZrC composites prepared by precursor infiltration and pyrolysis process. Journal of Materials Science and Technology, 2015, 31(1): 77.
[42] ZOU X, NI D, CHEN B, et al. Ablation behavior and mechanisms of 3D-C_f/Ta_0.8Hf_0.2C-SiC composite at temperatures up to 2500 °C. Journal of the European Ceramic Society, 2023, 43(4): 1284.
[43] ZHONG L, GUO L, WANG C, et al. Preparation and long-term ablation behavior of C_f-reinforced ZrC-SiC coated C/C-ZrC-SiC composite. Journal of the European Ceramic Society, 2024, 44(2): 693.
[44] CHEN B W, NI D W, LIAO C[J], et al. Long-term ablation behavior and mechanisms of 2D-C_f/ZrB₂-SiC composites at temperatures up to 2400 °C. Corrosion Science, 2020, 177: 108967.