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

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 583-594.DOI: 10.15541/jim20250424

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

赵彤彤¹(), 代吉祥¹(), 苏成¹, 师艳¹, 沙建军¹^,²

¹ 大连理工大学 1. 力学与航空航天学院
² 工业装备结构分析优化与CAE软件全国重点实验室, 大连 116024

收稿日期:2025-10-27 修回日期:2025-11-27 出版日期:2026-05-20 网络出版日期:2025-12-19
通讯作者: 代吉祥, 副教授. E-mail: jxdai@dlut.edu.cn
作者简介:赵彤彤(1998-), 女, 博士研究生. E-mail: zttz@mail.dlut.edu.cn
基金资助:
国防科技大学新型陶瓷纤维及其复合材料重点实验室(6142907230302);国家重点研发计划(2022YFB3707700)

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

ZHAO Tongtong¹(), DAI Jixiang¹(), SU Cheng¹, SHI Yan¹, SHA Jianjun¹^,²

¹ School of Mechanics and Aerospace Engineering, Dalian University of Technology, Dalian 116024, China
² State Key Laboratory of Structural Analysis, Optimization and CAE Software for Industrial Equipment, Dalian University of Technology, Dalian 116024, China

Received:2025-10-27 Revised:2025-11-27 Published:2026-05-20 Online:2025-12-19
Contact: DAI Jixiang, associate professor. E-mail: jxdai@dlut.edu.cn
About author:ZHAO Tongtong (1998-), female, PhD candidate. E-mail: zttz@mail.dlut.edu.cn
Supported by:
Science and Technology on Advanced Ceramic Fiber and Composites Laboratory, National University of Defence Technology(6142907230302);National Key R&D Program of China(2022YFB3707700)

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。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渗透-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。本研究为制备高性能一体化热防护结构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 formed 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 ℃ 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, ultra-high temperature ceramic, 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, 2026, 41(5): 583-594.

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, 2026, 41(5): 583-594.

图/表 15

图1 (a, c) CHS上表面和横切面的宏观形貌; (b, d)涂层和基体的XRD图谱

Fig. 1 (a, c) Macroscopic photographs of the upper surface and cross-section of CHS; (b, d) XRD patterns of the coating and substrate

图2 CHS的XRM图像切片

Fig. 2 XRM image slices of CHS (a) XZ plane; (b, c) YZ plane

图3 基于深度学习处理的CHS内部的三维XRM图像(a)、典型二维图像切片(b), 以及陶瓷基体和残留孔隙的含量随渗透深度的变化曲线(c)

Fig. 3 3D XRM image (a) and typical 2D image slices (b) of CHS processed using deep learning, along with the variation curves of ceramic matrix and residual pore content with penetration depth (c) Colorful figures are available on website

图4 CHS内部基体的微观形貌和EDS结果

Fig. 4 Microstructure and EDS results of the CHS internal matrix (a-c) Lower end region; (d-f) Upper end region

图5 CHS上表面涂层的微观形貌及EDS结果

Fig. 5 Microstructure and EDS results of the top surface coating on CHS (a-c) Coating surface; (d-f) Coating cross-section

图6 HfC-SiC-HfSi2涂层-基体一体化改性C/C复合材料的形成机制示意图

Fig. 6 Formation mechanism diagram of HfC-SiC-HfSi2 coating-matrix integrated modified C/C composites

图7 Hf-C、Si-C反应的吉布斯自由能随温度的变化曲线

Fig. 7 Gibbs free energy changes as a function of temperature for the Hf-C and Si-C reactions

图8 (a)试样烧蚀中心的温度曲线; (b)质量和线性烧蚀率; (c)试样烧蚀后的表面形貌

Fig. 8 (a) Temperature curves at the ablation center of the samples; (b) Mass and linear ablation rates; (c) Surface morphologies of the samples after ablation

图9 烧蚀试样表面的XRD图谱(a)及2θ=26°~34°范围的放大图谱(b)

Fig. 9 XRD patterns of the ablated samples surface (a) and enlarged patterns in the range of 2θ=26°-34° (b)

图10 烧蚀试样表面中心和边缘区域的微观形貌

Fig. 10 Micro-morphologies of the center and edge regions of the ablated samples surface (a-c) CHS-60; (d-f) CHS-180; (g-i) CHS-600

图11 试样烧蚀中心截面的微观形貌及EDS元素面分布图

Fig. 11 Micro-morphologies and EDS elemental mappings of the cross-section at the ablation center of the samples (a, a1) CHS-60; (b, b1) CHS-180; (c, c1) CHS-600

图12 CHS-3540的烧蚀中心温度曲线及试样和石墨夹具在烧蚀过程中(a)和烧蚀停止后(b)的状态图

Fig. 12 Temperature curve at the ablation center of CHS-3540 and state diagrams of the sample and graphite fixture during (a) and after (b) ablation

图13 CHS-3540烧蚀表面的XRD图谱

Fig. 13 XRD pattern of the CHS-3540 ablation surface

图14 CHS-3540烧蚀后的表面宏观形貌(a)和微观形貌(b~g)

Fig. 14 Macroscopic morphology (a) and microstructures (b-g) of CHS-3540 after ablation (b) Transition region; (c) Edge region; (d-f) HfO2 layer at ablation center; (g) Cross-section

图15 本工作与相关文献报道的线烧蚀率的比较[18,20,22 -23,25 -26,34 -44]

Fig. 15 Comparison of line ablation rates between this work and related literature[18,20,22 -23,25 -26,34 -44] Colorful figure is available on website

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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

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

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