1100 ℃水氧环境下Mini-SiCf/BN/SiC的基体/界面/纤维一体化氧化机制

doi:10.15541/jim20250249

无机材料学报 ›› 2026, Vol. 41 ›› Issue (3): 340-348.DOI: 10.15541/jim20250249 CSTR: 32189.14.jim20250249

1100 ℃水氧环境下Mini-SiC_f/BN/SiC的基体/界面/纤维一体化氧化机制

戚芳¹(), 刘辉¹, 吴郑敏¹, 陆毅¹, 吴雯雯², 王震¹()

1.乌镇实验室, 桐乡 314000
2.陕西师范大学物理学与信息技术学院, 西安 710000

收稿日期:2025-06-12 修回日期:2025-08-08 出版日期:2025-08-26 网络出版日期:2025-08-26
通讯作者: 王震, 研究员. E-mail: wangz@wuzhenlab.com
作者简介:戚芳(1996-), 女, 硕士研究生. E-mail: qif@wuzhenlab.com
基金资助:
国家重点研发计划(2022YFB3707700)

Matrix/Interface/Fiber Integrated Oxidation Mechanism of Mini-SiC_f/BN/SiC in Water-oxygen Environment at 1100 ℃

QI Fang¹(), LIU Hui¹, WU Zhengmin¹, LU Yi¹, WU Wenwen², WANG Zhen¹()

1. Wuzhen Laboratory, Tongxiang 314000, China
2. School of Physics and Information Technology, Shaanxi Normal University, Xi’an 710000, China

Received:2025-06-12 Revised:2025-08-08 Published:2025-08-26 Online:2025-08-26
Contact: WANG Zhen, professor. E-mail: wangz@wuzhenlab.com
About author:QI Fang (1996-), female, Master candidate. E-mail: qif@wuzhenlab.com
Supported by:
National Key R&D Program of China(2022YFB3707700)

摘要/Abstract

摘要：

SiC_f/SiC复合材料具备耐高温、抗氧化、高强度等特性, 在航空航天热防护领域具有重要应用前景。在服役条件下, 材料需长期承受热、水、氧等多种环境因素的耦合作用, 其失效机理和损伤规律极为复杂。本研究以SiC_f/BN/SiC迷你复合材料(Mini-SiC_f/BN/SiC)为试材, 通过多尺度宏/微观表征手段, 探究其在1100 ℃水氧耦合环境下的循环氧化行为, 重点分析基体/界面/纤维一体化氧化机制。结果表明: 氧化初期, 试材基体表面生成无定型SiO₂玻璃层, 表面相对光滑; 随着氧化过程的持续, SiO₂结晶度逐渐提高, 导致氧化层局部剥落, 表面粗糙度先减小后增大。X射线显微镜分析结果表明, 经循环氧化处理后, 试材内部产生大量微小缺陷, 缺陷总数呈数量级增加(约107倍), 小尺寸缺陷主要分布于基体表面, 且氧化产物对缺陷起到一定填充作用。试材拉伸性能在循环氧化前后未发生显著变化, 平均拉伸强度分别为(328.47±32.84)和(343.27±35.71) MPa, 这表明“强基体-弱界面”的协同氧化增韧机制仍有效。具体而言, 平行于纤维轴方向, 界面层和附近基体、纤维生成的SiO₂和硼硅酸盐玻璃能够填充缺陷; 垂直于纤维轴方向, 基体内形成的动态“外层多孔可牺牲层-中层致密SiO₂-内层SiC基体”三维防护屏障, 构成了基体/界面/纤维一体化氧化机制, 可显著缓解热-水-氧环境下循环氧化对材料的侵蚀。

关键词: Mini-SiC_f/BN/SiC, 循环氧化, 高温水氧环境, 多尺度表征, 氧化机制

Abstract:

SiC_f/SiC composites exhibit advantages such as high-temperature resistance, oxidation resistance and high strength, making them a “star” candidate material in the field of aerospace thermal protection. Under operational conditions, these materials are subjected to prolonged multiple coupled fields such as heat, water and oxygen, exhibiting complex failure mechanisms and damage evolution patterns. This study investigated the integrated oxidation mechanism of the matrix/interface/fiber in Mini-SiC_f/BN/SiC composites under cyclic oxidation at 1100 ℃ in a water-oxygen coupled environment by using multi-scale macro/micro characterization techniques. The results showed that during the initial oxidation stage, an amorphous SiO₂ glass layer with relatively smooth morphology formed on the material surface. However, with an increase in crystallinity, localized spallation occurred in the oxide layer, causing the surface roughness to initial decrease and subsequent increase. X-ray microscope results showed that numerous micro-defects were generated within the material after cyclic oxidation, and the number of defects increased by orders of magnitude (about 107 fold). Majority of these micro-defects were mainly distributed on the matrix surface, and the oxidation products played a certain filling role in these defects. The tensile strength showed no significant variation before ((328.47±32.84) MPa) and after ((343.27±35.71) MPa) cyclic oxidation, indicating continued effectiveness of the synergistic toughening mechanism of “strong matrix-weak interface”. These observations indicate that an integrated oxidation protection mechanism involving matrix, interface and fiber exists in the Mini-SiC_f/BN/SiC, which is predicated on the filling of defects by SiO₂ and borosilicate glass generated by its interface layer and adjacent matrix with fibers in the direction parallel to the fiber axis. Dynamic “outer porous sacrificial layer-middle dense SiO₂-inner SiC matrix” is a three-dimensional protective barrier of the matrix in the direction perpendicular to the fiber axis. This dual-protection system substantially alleviates material degradation under cyclic thermal water oxidative conditions.

Key words: Mini-SiC_f/BN/SiC, cyclic oxidation, high-temperature water-oxygen environment, multi-scale representation, oxidation mechanism

中图分类号:

TB332

戚芳, 刘辉, 吴郑敏, 陆毅, 吴雯雯, 王震. 1100 ℃水氧环境下Mini-SiC_f/BN/SiC的基体/界面/纤维一体化氧化机制[J]. 无机材料学报, 2026, 41(3): 340-348.

QI Fang, LIU Hui, WU Zhengmin, LU Yi, WU Wenwen, WANG Zhen. Matrix/Interface/Fiber Integrated Oxidation Mechanism of Mini-SiC_f/BN/SiC in Water-oxygen Environment at 1100 ℃[J]. Journal of Inorganic Materials, 2026, 41(3): 340-348.

图/表 14

图1 Mini-SiCf/BN/SiC的测试示意图

Fig. 1 Schematic diagrams of the test for Mini-SiCf/BN/SiC (a) Location of SEM test; (b) Tensile test specimen

图2 原始Mini-SiCf/BN/SiC的SEM照片(a, b)和EDS图谱(c)

Fig. 2 SEM images (a, b) and EDS pattern (c) of the original Mini-SiCf/BN/SiC composite

图3 Mini-SiCf/BN/SiC的质量变化与循环氧化时间的关系

Fig. 3 Relationship between mass change and cyclic oxidation time of Mini-SiCf/BN/SiC

图4 循环氧化不同时间的Mini-SiCf/BN/SiC表面SEM照片

Fig. 4 SEM images of Mini-SiCf/BN/SiC surface after cyclic oxidation for different time (a) 0 h; (b) 20 h; (c) 40 h; (d) 60 h; (e) 80 h; (f) 100 h

图5 循环氧化不同时间的Mini-SiCf/BN/SiC的表面形貌、三维图和粗糙度

Fig. 5 Surface morphologies, 3D images and roughnesses of Mini-SiCf/BN/SiC after cyclic oxidation for different time (a, b) 0 h; (c, d) 20 h; (e, f) 40 h; (g, h) 60 h; (i, j) 80 h; (k, l) 100 h

图6 循环氧化不同时间的Mini-SiCf/BN/SiC表面XRD图谱

Fig. 6 XRD patterns of Mini-SiCf/BN/SiC surface after cyclic oxidation for different time

图7 循环氧化不同时间的Mini-SiCf/BN/SiC中部(距端头10 mm)位置的SEM照片

Fig. 7 SEM images of the middle part of Mini-SiCf/BN/SiC (10 mm from the end) after cyclic oxidation for different time (a) 0 h; (b) 20 h; (c) 40 h; (d) 60 h; (e) 80 h; (f) 100 h

图8 氧化100 h后Mini-SiCf/BN/SiC近端头(距端头1 mm)位置的SEM照片和EDS图谱

Fig. 8 SEM images and EDS patterns of Mini-SiCf/BN/SiC near the tip (1 mm away from the tip) after oxidation for 100 h (a, b) SEM images; (c) EDS-spot 1; (d) EDS-spot 2

图9 氧化前Mini-SiCf/BN/SiC的XRM分析结果

Fig. 9 XRM analyses of Mini-SiCf/BN/SiC before oxidation (a) Overall diagram; (b-d) Slice diagrams; (e, f) Defect distribution diagrams; (g) Defect statistical diagram

图10 氧化100 h后Mini-SiCf/BN/SiC的XRM分析结果

Fig. 10 XRM analyses of Mini-SiCf/BN/SiC after oxidation for 100 h (a) Overall diagram; (b-d) Slice diagrams; (e, f) Defect distribution diagrams; (g) Defect statistical diagram

图11 氧化0和100 h后Mini-SiCf/BN/SiC的不同尺寸缺陷体积占比分析

Fig. 11 Analysis of the proportion of defect volume with different sizes in Mini-SiCf/BN/SiC after oxidation for 0 and 100 h

图12 1100 ℃水氧环境中Mini-SiCf/BN/SiC的氧化机制

Fig. 12 Oxidation mechanism of Mini-SiCf/BN/SiC in 1100 ℃ water oxygen environment

图13 氧化前后Mini-SiCf/BN/SiC的拉伸强度柱状图

Fig. 13 Tensile strength histogram of Mini-SiCf/BN/SiC before and after oxidation

图14 氧化前后Mini-SiCf/BN/SiC的拉伸断口形貌及EDS分析

Fig. 14 Tensile fracture morphologies and EDS analyses of Mini-SiCf/BN/SiC before and after oxidation (a, b) 0 h; (c-f) 100 h

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1100 ℃水氧环境下Mini-SiC_f/BN/SiC的基体/界面/纤维一体化氧化机制

Matrix/Interface/Fiber Integrated Oxidation Mechanism of Mini-SiC_f/BN/SiC in Water-oxygen Environment at 1100 ℃

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