原位SiC纳米线增韧SiC陶瓷的抗热震性能

肖元; 李露; 郑瑞晓; 马朝利

doi:10.13801/j.cnki.fhclxb.20220804.003

原位SiC纳米线增韧SiC陶瓷的抗热震性能

doi: 10.13801/j.cnki.fhclxb.20220804.003

肖元^1,,
李露²,
郑瑞晓¹,
马朝利^1, ,

1.
北京航空航天大学　材料科学与工程学院，空天先进材料与服役教育部重点实验室，北京100191
2.
北京航空航天大学　前沿科学技术创新研究院，北京100191

基金项目: 国家自然科学基金(51902010；92060301)；国家科技重大专项(J2019-VI-0001-0114)

详细信息

通讯作者:
马朝利，博士，教授，博士生导师，研究方向为轻质高强结构材料　E-mail: machaoli@buaa.edu.cn

中图分类号: V254.2
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出版历程
- 收稿日期: 2022-06-17
- 修回日期: 2022-07-18
- 录用日期: 2022-07-26
- 网络出版日期: 2022-08-05
- 刊出日期: 2022-08-22

Thermal-shock resistance of in-situ SiC nanowire-toughened SiC ceramics

XIAO Yuan^1
,,
LI Lu²,
ZHENG Ruixiao¹,
MA Chaoli^{1
, ,}

1.
Key Laboratory of Aerospace Advanced Materials and Performance of Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191, China
2.
Research Institute for Frontier Science, Beihang University, Beijing 100191, China

Funds: National Natural Science Foundation of China（51902010, 92060301）；National Major Science and Technology Projects of China (J2019-VI-0001-0114)

摘要

摘要: SiC陶瓷的本征脆性及其在高低温交变环境中抗热震能力的不足已成为制约其广泛应用的关键问题之一。本文以聚碳硅烷为前驱体、二茂铁为催化剂，通过前驱体转化法在制备低密度SiC陶瓷的同时在陶瓷中原位合成SiC纳米线，并采用前驱体浸渍裂解工艺将低密度陶瓷进一步致密化制备原位SiC纳米线增韧SiC陶瓷。实验结果表明，引入原位SiC纳米线后，SiC陶瓷的抗热震性能显著提升，经历30次“室温↔1500℃”的热震循环氧化后其氧化增重率仅为2.53%，相较于纳米线改性前的SiC陶瓷氧化增重率下降了59%。相应的微结构分析表明，合成的SiC纳米线为β-SiC晶型，其中包含部分堆垛层错。纳米线沿<111>方向择优生长，其生长遵循典型的“气-液-固”生长机制。SiC纳米线主要通过纳米线桥连和拔出增韧机制缓解陶瓷制备及高低温交变过程中产生的应力集中，减少裂纹数量和尺寸，进而提升陶瓷断裂韧性和抗热震性能。引入SiC纳米线后，SiC陶瓷内部平均裂纹长度由27.7 μm下降至18.2 μm，断裂韧性由3.76 MPa·m^1/2增加至7.83 MPa·m^1/2。
- SiC陶瓷 /
- 原位SiC纳米线 /
- 生长机制 /
- 聚碳硅烷 /
- 抗热震性能
Abstract: The brittleness and insufficient thermal-shock resistance are the critical problems for the extensive applications of SiC ceramics. Low-density SiC ceramics decorated with in-situ SiC nanowires were fabricated via the pyrolysis of polycarbosilane assisted by ferrocene. They were further densified by the technique of precursor infiltration and pyrolysis to prepare in-situ SiC nanowire-toughened SiC ceramics. The experimental results showed that, compared with the SiC ceramics without nanowires, the thermal shock resistance of the in-situ SiC nanowire-toughened SiC ceramics was improved significantly, whose oxidation mass gain was only 2.53% and decreased by 59% after 30 thermal cycles between room temperature and 1500 ℃. The corresponding microstructural analysis indicated that the synthesized SiC nanowires were β-SiC and contained some stacking faults. The β-SiC nanowires grew along the preferential orientation of <111> and its growth was governed by a vapor-liquid-solid mechanism. The in-situ SiC nanowires could effectively alleviate the stress concentration due to the ceramic preparation and the thermal cycles between high and low temperatures. The improved fracture toughness and thermal-shock resistance could be attributed to the toughening mechanism including nanowire bridging and pull-out, as well as the decrease of crack number and size in SiC ceramics. After the introduction of SiC nanowires, the average crack length of SiC ceramics decreased from 27.7 μm to 18.2 μm, and the fracture toughness increased from 3.76 MPa·m^1/2 to 7.83 MPa·m^1/2.
- SiC ceramic /
- in-situ SiC nanowires /
- growth mechanism /
- polycarbosilane /
- thermal shock resistance

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图 1 原位SiC纳米线增韧SiC陶瓷的制备过程示意图

Figure 1. Preparation schematic of the in-situ SiC nanowire-toughened SiC ceramic

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图 2 合成SiC纳米线和SiC陶瓷的XRD图谱

Figure 2. XRD patterns of the as-synthesized SiC nanowires and SiC ceramic

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图 3 原位SiC纳米线多孔层的SEM图像：(a) 表面；(b) 截面

Figure 3. SEM images of the in-situ SiC nanowire porous layer: (a) Surface; (b) Cross-section

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图 4 合成SiC纳米线的TEM结果：(a) 单根纳米线的明场像(BF)图像和相应的SAED花样；(b) 纳米线的HRTEM图像；(c) 纳米线尖端催化剂液滴的BF图像；(d) 催化剂液滴的EDS光谱

Figure 4. TEM results of the as-synthesized SiC nanowires: (a) Bright field (BF) image of a single nanowire and the corresponding SAED pattern; (b) HRTEM image of the nanowire; (c) BF image of a catalyst droplet attached at the tip of a nanowire; (d) EDS spectrum of the catalyst droplet

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图 5 3次和6次“浸渍-裂解”循环后纳米线增韧SiC陶瓷的形貌和元素分布：(a) 3次循环后的低倍表面SEM图像；(b) 3次循环后的高倍表面SEM图像；(c) 6次循环后的低倍表面SEM图像；(d) 6次循环后的高倍截面SEM图像；(e) 图5(c)对应的氧元素面扫图

Figure 5. Morphologies and element distribution of the nanowire-toughened SiC ceramic after 3 and 6 cycles of “infiltration-pyrolysis”: (a) Low-magnification surface SEM image after 3 cycles; (b) High-magnification surface SEM image after 3 cycles; (c) Low-magnification surface SEM image after 6 cycles; (d) High-magnification cross-sectional SEM image after 6 cycles; (e) Corresponding element map of oxygen in Fig. 5(c)

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图 6 引入纳米线前后SiC陶瓷的表面形貌：(a) 未引入SiC纳米线；(b) 引入原位SiC纳米线

Figure 6. Surface SEM images of the SiC ceramics before and after the introduction of nanowires: (a) Without SiC nanowires; (b) With in-situ SiC nanowires

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图 7 未引入和引入SiC纳米线的SiC陶瓷进行显微硬度测试后的表面形貌：(a) 未引入SiC纳米线；(b) 引入原位SiC纳米线

Figure 7. Surface SEM images of the SiC ceramics without/with nanowires after microhardness testing: (a) Without SiC nanowires; (b) With in-situ SiC nanowires

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图 8 SiC陶瓷经历“室温↔1500℃”热震后的质量变化曲线

Figure 8. Mass change curves of the SiC ceramics during thermal shock between room temperature and 1 500 ℃

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图 9 30次热震后SiC陶瓷的表面SEM图像：(a)未引入SiC纳米线；(b)引入原位SiC纳米线

Figure 9. Surface SEM images of the SiC ceramics after 30 thermal shock: (a) Without SiC nanowires; (b) With in-situ SiC nanowires

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图 10 原位SiC纳米线增韧SiC陶瓷经历30次热震后的断口图像：(a) SiC陶瓷表面的部分氧化纳米线；(b) SiC陶瓷内部的未氧化纳米线

Figure 10. Fracture surface images of the in-situ SiC nanowire-toughened SiC ceramic after 30 thermal shock cycles: (a) Partially-oxidized nanowires in the surface zone of SiC ceramic; (b) Unoxidized nanowires in the internal zone of SiC ceramic

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图 11 原位SiC纳米线增韧SiC陶瓷的增韧机制示意图

Figure 11. Schematic diagram of toughening mechanism for in-situ SiC nanowires toughening SiC ceramics

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