C/CA表面陶瓷-树脂涂层的简易制备与中温抗氧化性能

doi:10.15541/jim20250103

无机材料学报 ›› 2026, Vol. 41 ›› Issue (3): 401-412.DOI: 10.15541/jim20250103 CSTR: 32189.14.10.15541/jim20250103

• 研究快报 • 上一篇

C/CA表面陶瓷-树脂涂层的简易制备与中温抗氧化性能

田洪旺¹^,²(), 罗龙飞³, 胡成龙¹(), 闫猛¹, 庞生洋¹, 李建¹, 汤素芳¹

1.中国科学院金属研究所, 沈阳 110016
2.中国科学技术大学材料科学与工程学院, 沈阳 110016
3.西安航天复合材料研究所, 西安 710025

收稿日期:2025-03-11 修回日期:2025-05-19 出版日期:2025-05-22 网络出版日期:2025-05-22
通讯作者: 胡成龙, 研究员. E-mail: clhu10s@imr.ac.cn
作者简介:田洪旺(1999-), 男, 硕士研究生. E-mail: hwtian22s@imr.ac.cn

Facile Fabrication of Ceramic-resin Coatings on C/CA Composites for Oxidation Protection at Medium Temperatures

TIAN Hongwang¹^,²(), LUO Longfei³, HU Chenglong¹(), YAN Meng¹, PANG Shengyang¹, LI Jian¹, TANG Sufang¹

1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3. Xi’an Aerospace Composites Research Institute, Xi’an 710025, China

Received:2025-03-11 Revised:2025-05-19 Published:2025-05-22 Online:2025-05-22
Contact: HU Chenglong, professor. E-mail: clhu10s@imr.ac.cn
About author:TIAN Hongwang (1999-), male, Master candidate. E-mail: hwtian22s@imr.ac.cn
Supported by:
National Natural Science Foundation of China(52272075);National Natural Science Foundation of China(52472053);Research Fund of Youth Innovation Promotion Association of CAS, China(2021190);Defense Industrial Technology Development Program(JCKY2021130B007)

摘要/Abstract

摘要：

碳纤维增强碳气凝胶(C/CA)复合材料是同时满足隔热和承载应用需求的最具潜力的候选材料之一。在C/CA上制备抗氧化涂层用于解决其易氧化问题, 是促进其在氧化环境中应用的重要方法。然而, 目前已报道的C/CA抗氧化涂层主要用于提升材料的烧蚀性能, 且涂层制备工艺常涉及高温热处理过程, 这会导致C/CA热导率增加, 进而降低隔热效果。本研究在室温下采用简单的浆料刷涂-干燥方法, 在C/CA上制备了一系列陶瓷-树脂涂层, 并研究了酚醛树脂含量对涂层结构、残余应力、热冲击以及氧化行为的影响。结果表明, 得益于树脂的黏接作用和固化收缩作用, PR-7.5涂层(料浆中酚醛树脂质量分数为7.5%)结合强度与基底本征断裂强度相近, 且具有0.853 GPa的残余压应力, 显著提升了其热震性能; 而进一步提高树脂含量(PR-10.0, 料浆中酚醛树脂质量分数为10.0%), 涂层因树脂不均匀固化导致收缩不一致而产生了残余拉应力, 热震时易开裂。实验结果显示, PR-7.5在800 ℃下氧化100 min、1000 ℃下氧化120 min以及1200 ℃下氧化120 min后失重率分别为17.46%、8.15%和3.15%; 而没有涂层的C/CA复合材料在800 ℃下氧化20 min后失重率高达44.60%。本工作为提高C/CA的抗氧化性能提供了一种全新且简单的途径, 拓展了其在温和氧化环境中的应用。

关键词: C/CA复合材料, 涂层, 氧化, 残余应力, 界面结合

Abstract:

Carbon fiber-reinforced carbon aerogel (C/CA) composites are one of the most promising candidates for applications requiring both thermal insulation and load bearing capabilities. The preparation of anti-oxidation coatings on C/CA to address its susceptibility to oxidation is a feasible approach to promote its application in oxidative environments. However, the currently reported coatings on C/CA mainly focus on improving the ablation performance and coating preparation process typically necessitating high-temperature heat treatment. This procedure can increase its thermal conductivity and reduce its thermal insulation ability. In this study, a series of ceramic-resin coatings were fabricated on C/CA through a simple slurry brushing-drying approach at room temperature. The effects of phenolic resin content on the coating structure, residual stress, thermal shock, and oxidation behaviors were investigated. Due to the adhesive properties and curing-induced shrinkage, the PR-7.5 coating (containing 7.5% (in mass) phenolic resin in the slurry) exhibits bonding strength close to fracture strength of the substrate and residual compressive stress of 0.853 GPa, which is beneficial for resisting thermal shock cracking. However, excessive resin content (PR-10.0 containing 10.0% (in mass) phenolic resin in the slurry) induces tensile stress due to uneven curing shrinkage, thereby leading to thermal shock cracking. Meanwhile, oxidation tests reveal significantly reduced weight losses for PR-7.5 (17.46% at 800 ℃/100 min, 8.15% at 1000 ℃/120 min, 3.15% at 1200 ℃/120 min) versus uncoated C/CA’s 44.60% loss at 800 ℃/20 min. This work provides a brand-new and simple approach to improving the anti-oxidation performance of C/CA and expands its application in mild oxidative environments.

Key words: C/CA composite, coating, oxidation, residual stress, interfacial bonding

中图分类号:

TQ174

田洪旺, 罗龙飞, 胡成龙, 闫猛, 庞生洋, 李建, 汤素芳. C/CA表面陶瓷-树脂涂层的简易制备与中温抗氧化性能[J]. 无机材料学报, 2026, 41(3): 401-412.

TIAN Hongwang, LUO Longfei, HU Chenglong, YAN Meng, PANG Shengyang, LI Jian, TANG Sufang. Facile Fabrication of Ceramic-resin Coatings on C/CA Composites for Oxidation Protection at Medium Temperatures[J]. Journal of Inorganic Materials, 2026, 41(3): 401-412.

图/表 15

Fig. 1 Surface and cross-sectional morphologies of (a) PR-0, (b) PR-5.0, (c) PR-7.5, and (d) PR-10.0 Insets showing the corresponding cross-sectional morphologies

Fig. 2 Weight loss of C/CA with different coatings during thermal shock at 1200 ℃

Fig. 3 (a-d) Surface morphologies of PR-0, PR-5.0, PR-7.5, and PR-10.0 after thermal shock; (c1-c3) Surface microstructures under high magnification and corresponding elemental analyses; (e, e1) Cross-sectional morphologies of PR-7.5

Fig. 4 (a) XRD patterns near 2θ=39° of different coatings, and (b) residual stress of the coating calculated according to the shift of diffraction peaks in (a)

Fig. 5 Weight loss of the C/CA with PR-7.5 during oxidation at 800-1200 ℃

Fig. 6 Surface morphologies of the oxidized PR-7.5 at (a) 800, (b) 1000 and (c) 1200 ℃

Fig. S1 Macrophotograph of the coated C/CA panel with a size of 300 mm×300 mm×25 mm

Fig. S2 XRD patterns of C/CA without and with different coatings

Fig. S3 Macroscopic surface morphologies of the different coatings after thermal shock from 1200 ℃ to room temperature (a) PR-0; (b) PR-5.0; (c) PR-7.5; (d) PR-10.0

Fig. S4 Thermogravimetric analyses of ceramics in the coating

Fig. S5 (a, b) Surface morphologies of the sample after the tensile test, and (c) tensile curves of the C/CA substrate and the coated C/CA

Table S1 Fitting results of oxidation kinetics equation parameters of PR-0, PR-5.0, PR-7.5, and PR-10.0 at 800, 1000 and 1200 ℃

Temperature/℃	Sample	a/(×10^-2, min^-1)	b	R²	k/(×10^-3, s^-1)	lnk
800	PR-0	43.45	-4.305	0.9974	7.2417	-4.9279
	PR-5.0	35.9	8.9301	0.9996	5.9833	-5.1188
	PR-7.5	17.42	-1.3518	0.9974	2.9033	-5.8419
	PR-10.0	40.84	8.8932	0.9948	6.8067	-4.9899
1000	PR-0	66.32	-4.2528	0.9999	11.0533	-4.5050
	PR-5.0	8.75	0.9611	0.9611	1.4583	-6.5305
	PR-7.5	5.15	0.8934	0.8934	0.8583	-7.0605
	PR-10.0	18.68	5.5384	0.9951	3.1133	-5.7721
1200	PR-0	81.66	-9.239	0.9996	13.61	-4.2970
	PR-5.0	10.72	6.0556	0.8625	1.7867	-6.3274
	PR-7.5	2.37	0.0858	0.9112	0.395	-7.8366
	PR-10.0	35.01	3.0509	0.9928	5.835	-5.1439

Fig. S6 Weight loss of the C/CA with different coatings under oxidation tests in the temperature range of 800-1200 ℃ (a) PR-0; (b) PR-5.0; (c) PR-7.5; (d) PR-10.0

Fig. S7 Oxidation rate curves with 1/T for the different coated C/CA

Fig. S8 (a) Cross-sectional microstructure of PR-7.5 and (b, c) elemental line scanning of C and Si in (a)

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C/CA表面陶瓷-树脂涂层的简易制备与中温抗氧化性能

Facile Fabrication of Ceramic-resin Coatings on C/CA Composites for Oxidation Protection at Medium Temperatures

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