前驱体衍生ZrB2/(SiC-AlN)陶瓷复合材料的制备及性能研究

doi:10.15541/jim20260026

无机材料学报 ›› 2026, Vol. 41 ›› Issue (9): 1339-1348.DOI: 10.15541/jim20260026

• 研究快报 • 上一篇

前驱体衍生ZrB₂/(SiC-AlN)陶瓷复合材料的制备及性能研究

周岩¹^,²(), 刘骐恺², 夏爱东²^,³, 张步豪²^,⁴(), 殷杰²^,³(), 黄政仁²^,³

¹ 上海大学材料科学与工程学院, 上海 200444
² 中国科学院上海硅酸盐研究所, 上海 201899
³ 中国科学院大学材料科学与光电技术学院, 北京 100864
⁴ 诺丁汉大学工程学院, 诺丁汉 NG7 2RD

收稿日期:2026-01-16 修回日期:2026-03-04 出版日期:2026-09-20 网络出版日期:2026-03-18
通讯作者: 张步豪, 副研究员. E-mail: buhaozhang@hotmail.com;
殷杰, 研究员. E-mail: jieyin@mail.sic.ac.cn
作者简介:周岩(2002-), 男, 硕士研究生. E-mail: zyan@hnu.edu.cn

Polymer-derived ZrB₂/(SiC-AlN) Ceramic Composites: Fabrication and Performance

ZHOU Yan¹^,²(), LIU Qikai², XIA Aidong²^,³, ZHANG Buhao²^,⁴(), YIN Jie²^,³(), HUANG Zhengren²^,³

¹ School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
² Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
³ College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100864, China
⁴ Faculty of Engineering, University of Nottingham, Nottingham NG7 2RD, UK

Received:2026-01-16 Revised:2026-03-04 Published:2026-09-20 Online:2026-03-18
Contact: ZHANG Buhao, associate professor. E-mail:buhaozhang@hotmail.com;YIN Jie, professor. E-mail:jieyin@mail.sic.ac.cn
About author:ZHOU Yan (2002-), male, Master candidate. E-mail: zyan@hnu.edu.cn
Supported by:
National Natural Science Foundation of China(U22A20129);National Natural Science Foundation of China(U23A2056);National Key R&D Program of China(2022YFB3706300)

摘要/Abstract

摘要：

针对高超声速飞行器热防护系统等极端高温结构应用需求, 本研究以商用聚碳硅烷与聚硼锆氧烷为前驱体, 通过前驱体转化结合热压烧结工艺, 在1950 ℃成功制备了ZrB₂/(SiC-AlN)陶瓷复合材料。X射线衍射结果显示, 烧结后产物中形成六方SiC相与ZrB₂相, 未出现明显的AlN特征峰, 证实AlN已固溶于SiC基体中, 形成了SiC-AlN固溶体。显微结构观察结果表明, 前驱体衍生的ZrB₂均匀分散在SiC-AlN基体中, 不仅促进了烧结致密化, 还能有效抑制基体晶粒生长。本研究还系统分析了前驱体衍生ZrB₂含量对复合材料物相演变、显微结构特征、致密化行为以及力学性能的影响。当ZrB₂和AlN质量分数分别为25%和10%时, 复合材料表现出最佳综合性能, 其开口气孔率为0.6%, 抗弯强度达(407±14) MPa, 断裂韧性为(5.8±0.1) MPa·m^1/2。同时, 在800~1000 ℃静态空气中还表现出良好的短期抗氧化性能。结果表明, 基于前驱体法引入ZrB₂可有效调控聚合物衍生陶瓷基SiC-AlN复合材料的微观结构并提升其综合性能。

关键词: 前驱体衍生陶瓷, 纳米复合材料, SiC-AlN固溶体, 韧性, 强度

Abstract:

In response to the demanding requirements of extreme high-temperature structural applications, such as thermal protection systems for hypersonic vehicles, ZrB₂/(SiC-AlN) ceramic composites were fabricated via a precursor- derived route using commercially available polycarbosilane and polyborozirconoxane, followed by hot-press sintering at 1950 ℃. X-ray diffraction results indicated the formation of hexagonal SiC and ZrB₂ phases after sintering, while no distinct AlN diffraction peaks were observed due to the formation of a SiC-AlN solid solution. Microstructural observations revealed that in situ formed ZrB₂ was uniformly dispersed within the SiC-AlN matrix, contributing to improved densification and inhibition of grain growth. The effects of precursor-derived ZrB₂ content on phase composition, microstructure, densification behavior, and mechanical properties of the composites were systematically investigated. Among the series of samples, the composite containing 25% ZrB₂ and 10% AlN (in mass) exhibited the lowest open porosity (0.6%), the highest flexural strength ((407±14) MPa), and the maximum fracture toughness ((5.8±0.1) MPa·m^1/2). This composition also exhibited effective short-term oxidation resistance in static air over the temperature range of 800-1000 ℃. The results demonstrate that the precursor-derived introduction of ZrB₂ is an effective approach to tailor microstructure and enhance the overall performance of polymer-derived SiC-AlN ceramic composites.

Key words: precursor-derived ceramic, nanocomposite, SiC-AlN solid solution, toughness, strength

中图分类号:

TQ174

周岩, 刘骐恺, 夏爱东, 张步豪, 殷杰, 黄政仁. 前驱体衍生ZrB₂/(SiC-AlN)陶瓷复合材料的制备及性能研究[J]. 无机材料学报, 2026, 41(9): 1339-1348.

ZHOU Yan, LIU Qikai, XIA Aidong, ZHANG Buhao, YIN Jie, HUANG Zhengren. Polymer-derived ZrB₂/(SiC-AlN) Ceramic Composites: Fabrication and Performance[J]. Journal of Inorganic Materials, 2026, 41(9): 1339-1348.

图/表 12

Fig. 1 XRD patterns of the samples pyrolyzed at different temperatures

Fig. 2 XRD patterns of hot-pressed ZrB2/(SiC-AlN) ceramic composites (P90A10, P65A10Z25, and P45A10Z45) at 1950 ℃

Fig. 3 (a, e, i) Polished surfaces, (b, c, f, g, j, k) fractured surfaces and (d, h, l) SiC grain size distributions of hot-pressed ZrB2/(SiC-AlN) ceramics

Table 1 Properties of the precursor-derived ZrB2/(SiC-AlN) composites

Label	Open porosity/%	Flexural strength/MPa	Fracture toughness/ (MPa·m^1/2)
P90A10	2.9	368±8	4.5±0.1
P65A10Z25	0.6	407±14	5.8±0.1
P45A10Z45	1.1	328±5	3.7±0.3

Fig. 4 (a, b) SEM images and (c-h) elemental mappings of the polished surface of P65A10Z25

Fig. 5 (a) Morphology and (b-f) elemental mappings of the fracture surface of SiC-AlN solid-solution

Fig. 6 Crack propagation path and characteristic features in P65A10Z25

Fig. 7 Oxidation results of the samples at different temperatures (a-c) Phase analyses of oxide layers; (d-f) Variation of unit area mass change with oxidation time

Fig. 8 Surface and macro morphologies (insets) of the samples after oxidation at different temperatures (a-c) P90A10: (a) 800 ℃, (b) 1000 ℃, (c) 1200 ℃; (d-f) P65A10Z25: (d) 800 ℃, (e) 1000 ℃, (f) 1200 ℃; (g-i) P45A10Z45: (g) 800 ℃, (h) 1000 ℃, (i) 1200 ℃

Fig. S1 Thermal analysis of the ZrB2 precursors

Fig. S2 Point-scan element distribution of the P90A10 sample

Fig. S3 Element distribution of the P65A10Z25 sample during surface scanning and point scanning

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前驱体衍生ZrB₂/(SiC-AlN)陶瓷复合材料的制备及性能研究

Polymer-derived ZrB₂/(SiC-AlN) Ceramic Composites: Fabrication and Performance

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