反应熔渗法制备Hf-Si基涂层-基体一体化改性C/C复合材料的微观结构及烧蚀性能

doi:10.15541/jim20250424

摘要/Abstract

摘要： 为提升C/C复合材料在超高温长时环境下的抗烧蚀性能,本研究采用非包埋的反应熔渗法,成功制备了Hf-Si基涂层-基体一体化改性C/C复合材料。微观结构分析表明,涂层和基体主要由HfC、SiC和HfSi₂相构成,两者通过化学反应形成紧密结合的界面。材料内部基体的致密度及组分构成沿渗透方向呈现梯度分布：靠近入渗端孔隙填充致密,基体相以HfC-HfSi₂为主;远离入渗端残存较多孔隙,基体相以SiC和Si-HfSi₂两相共晶组织为主。表面涂层结构连续且致密,厚度约120 μm,其主要由SiC外层和HfC-HfSi₂-SiC内层构成。对复合材料反应形成机制的深入探究表明,HfC-SiC-HfSi₂涂层-基体一体化结构是熔体浸渗-反应与气相渗透-沉积协同作用的结果。氧乙炔烧蚀测试结果表明,该复合材料具有优异的抗高温烧蚀性能。在2500 ℃下烧蚀考核60、180、600和3540 s后,材料的线烧蚀率分别为-3.52、-1.35、-0.85和 0.118 μm/s。复合材料优异的抗烧蚀性能源于表面多组分涂层协同氧化生成的连续致密HfO₂保护层,以及涂层下方基体氧化生成的HfO₂-SiO₂-HfSiO₄多相混合氧化物层。两者共同作用,有效抑制了氧气向内扩散,从而显著延缓了复合材料内部的氧化烧蚀进程。本研究为高性能一体化热防护结构的制备提供了一种可行的技术策略。

关键词: 反应熔渗法, 超高温陶瓷, 涂层-基体一体化, 微观结构, 抗烧蚀性能

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

中图分类号:

TB332

赵彤彤, 代吉祥, 苏成, 师艳, 沙建军. 反应熔渗法制备Hf-Si基涂层-基体一体化改性C/C复合材料的微观结构及烧蚀性能[J]. 无机材料学报, DOI: 10.15541/jim20250424.

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.

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