SiCp掺杂Cf/Li2O-Al2O3-SiO2复合材料耐烧蚀性能研究

doi:10.15541/jim20240493

无机材料学报 ›› 2025, Vol. 40 ›› Issue (10): 1153-1162.DOI: 10.15541/jim20240493

SiC_p掺杂C_f/Li₂O-Al₂O₃-SiO₂复合材料耐烧蚀性能研究

林元伟¹(), 景昭², 陈鹤拓¹(), 李佳恒¹^,⁴, 覃显鹏¹, 周国红¹^,³(), 王士维¹^,³

¹ 中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 200050
² 北京航天长征飞行器研究所, 北京 100076
³ 中国科学院大学材料与光电研究中心, 北京 100049
⁴ 上海大学微电子学院, 上海 200444

收稿日期:2024-11-26 修回日期:2025-02-19 出版日期:2025-02-25 网络出版日期:2025-02-25
通讯作者: 陈鹤拓, 副研究员. E-mail: chenhetuo@mail.sic.ac.cn;
周国红, 研究员. E-mail: sic_zhough@mail.sic.ac.cn
作者简介:林元伟(1997-), 男, 硕士. E-mail: linyuanwei19@mails.ucas.ac.cn

Ablative Properties of SiC_p Doped C_f/Li₂O-Al₂O₃-SiO₂ Composites

LIN Yuanwei¹(), JING Zhao², CHEN Hetuo¹(), LI Jiaheng¹^,⁴, QIN Xianpeng¹, ZHOU Guohong¹^,³(), WANG Shiwei¹^,³

¹ State Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
² Beijing Institute of Space Long March Vehicle, Beijing 100076, China
³ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
⁴ School of Microelectronics, Shanghai University, Shanghai 200444, China

Received:2024-11-26 Revised:2025-02-19 Published:2025-02-25 Online:2025-02-25
Contact: CHEN Hetuo, associate professor. E-mail: chenhetuo@mail.sic.ac.cn;
ZHOU Guohong, professor. E-mail: sic_zhough@mail.sic.ac.cn
About author:LIN Yuanwei (1997-), male, Master. E-mail: linyuanwei19@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(U23A6014);National Natural Science Foundation of China(52103357)

摘要/Abstract

摘要：

在高热流密度烧蚀环境中, 飞行器的表面温度迅速升高, 导致传统高导热材料无法有效保护内部金属部件。本研究通过浆液浸渍缠绕和热压烧结法制备了SiC颗粒(SiC_p)掺杂的连续碳纤维增强低导热Li₂O-Al₂O₃-SiO₂(C_f/LAS)玻璃陶瓷复合材料, 研究了基体结晶度对超高热流密度下复合材料烧蚀性能的影响规律。利用复合材料中SiO₂气化吸热和低导热的特性, 有效降低了复合材料表面和内部温度, 从而保障了飞行器和电子器件的安全运行。结果显示, 在20 MW/m²热流密度下, 10%(质量分数)SiC_p掺杂的复合材料平均线性烧蚀率显著降低。透射电镜结果表明, 掺杂后的玻璃基体结晶度提高, 内应力降低, 晶格畸变减少, 从而增强了复合材料的高温性能。然而, 当SiC掺杂量过高时, 结晶度降低, 烧蚀性能变差。最终, 在30 MW/m²热流密度下, 10%(质量分数)SiC_p掺杂的C_f/LAS复合材料的平均线性烧蚀率与商用碳/碳复合材料相当, 且具有较低的导热性和较高的抗弯强度。这种新型高性能C_f/LAS复合材料价格低廉、周期短, 适合大规模生产, 有望广泛应用于高超音速飞行器耐烧蚀部件。

关键词: 耐烧蚀C_f/LAS复合材料, SiC掺杂, 玻璃基体结晶度, 长程有序

Abstract:

In a high heat flux ablative environment, the surface temperature of aircraft rises rapidly, leading to traditional high thermal conductivity materials being ineffective at protecting internal metal components. In this study, continuous carbon fiber reinforced Li₂O-Al₂O₃-SiO₂ (C_f/LAS) glass ceramic composites doped with SiC particles (SiC_p) were prepared by slurry immersion winding and hot pressing sintering. Effect of matrix crystallinity on ablative properties of the composites under ultra-high heat flux was investigated. By utilizing heat absorption and low thermal conductivity characteristics associated with SiO₂ gasification within composite materials, both surface and internal temperatures of these materials are effectively reduced, thereby ensuring the safe operation of aircraft and electronic devices. Results indicate that the average linear ablation rate of composites doped with 10% (in mass) of SiC_p significantly decreases at a heat flux of 20 MW/m². Transmission electron microscope observation reveals that the doped glass matrix exhibits increased crystallinity, reduced internal stress, and minimized lattice distortion, thereby enhancing the composites’ high-temperature performance. However, excessive SiC_p doping leads to reduced crystallinity and deteriorated ablation performance. Ultimately, the average linear ablation rate of C_f/LAS composites with 10% (in mass) SiC_p at 20 MW/m² heat flux is comparable to that of commercial carbon/carbon composites, accompanied by providing lower thermal conductivity and higher bending strength. This novel high-performance C_f/LAS composite is cost-effective, short-cycled, and suitable for mass production, offering promising potential for widespread application in ablation-resistant components of hypersonic vehicles.

Key words: ablation-resistant C_f/LAS composite, SiC doping, crystallinity of glass matrix, long-range ordered

中图分类号:

TB35

林元伟, 景昭, 陈鹤拓, 李佳恒, 覃显鹏, 周国红, 王士维. SiC_p掺杂C_f/Li₂O-Al₂O₃-SiO₂复合材料耐烧蚀性能研究[J]. 无机材料学报, 2025, 40(10): 1153-1162.

LIN Yuanwei, JING Zhao, CHEN Hetuo, LI Jiaheng, QIN Xianpeng, ZHOU Guohong, WANG Shiwei. Ablative Properties of SiC_p Doped C_f/Li₂O-Al₂O₃-SiO₂ Composites[J]. Journal of Inorganic Materials, 2025, 40(10): 1153-1162.

图/表 11

Fig. 1 Characterizations of Cf/LAS-SC composites (a) XRD patterns; (b) XRD refined patterns of Cf/LAS-SC3; (c) Mass percentages of different phases obtained by XRD refinement (c-SC indicates crystalline SiC and c-LAS indicates crystalline LAS); (d) Density (ρ) and relative density (ρr)

Fig. 2 Cross-sectional morphologies of Cf/LAS-SC (a) Cf/LAS; (b) Cf/LAS-SC1; (c) Cf/LAS-SC2; (d) Cf/LAS-SC3; (e) Cf/LAS-SC4

Fig. 3 Cross-sectional microscopic morphology and EDS mappings of Cf/LAS after ablation

Fig. 4 Cross-sectional microscopic morphology and EDS mappings of Cf/LAS-SC1 after ablation

Fig. 5 TEM characterizations of Cf/LAS composite material along the [$1\bar{2}1$] zone axis (a) High-resolution transmission electron microscopy (HRTEM) image; (b) Images for selected regions obtained locally enlarged after the corresponding region’s fast Fourier transform (FFT); (c-e) Strain distribution obtained by geometric phase analysis (GPA) of FFT

Fig. 6 TEM characterizations of Cf/LAS-SC1 composite material along the [$1\bar{2}1$] zone axis (a) HRTEM image; (b) Images for selected regiosn obtained locally enlarged after the corresponding region’s FFT; (c-e) Strain distribution obtained by GPA of FFT

Fig. 7 X-CT 3D reconstructions of (a) Cf/LAS and (b) Cf/LAS-SC1 after ablation

Fig. 8 (a) Average linear ablation rate with insets showing photographs of Cf/LAS-SC1 (left) and Cf/LAS (right)); (b) Surface temperature of Cf/LAS-SC; (c, d) Schematic diagrams of (c) oxygen molecule direct contact ablation and (d) oxygen ion diffusion ablation mechanism, respectively

Table 1 Properties of Cf/C and Cf/LAS ablative composites[29-31]

Composition	ρ/ (g·cm^-3)	λ/ (W·m^-1·K^-1)	Ablation at high heat flux			Ref.
Composition	ρ/ (g·cm^-3)	λ/ (W·m^-1·K^-1)	Ablation rate/ (mm·s^-1)	Test environments	Ablation time/s	Ref.
C_f/C	1.85	45-68 (25-800 ℃)	-	Oxyacetylene torch with a heat flux of 3.9 MW/m²	60	[28]
	1.80	-	1.2-1.4	Stagnation ablation by high temperature air ionization jet	3	[29]
	1.80	-	0.114	Nitrogen plasma jet with a heat flux of ~25 MW/m²	20	[30]
	1.80	-	0.699	Stagnation ablation by air plasma flame with a heat flux of 22.1 MW/m²	3	[31]
	-	-	0.245	Liquid oxygen-kerosene, and the heat flux at 30 MW/m²	10	This work
C_f/LAS-SiC1	2.03	2.2-3.4 (25-1000 ℃)	0.35	Liquid oxygen-kerosene, and the heat flux at 20 MW/m²	10	This work
C_f/LAS-SiC1	2.03	2.2-3.4 (25-1000 ℃)	0.70	Liquid oxygen-kerosene, and the heat flux at 30 MW/m²	10	This work

Fig. 9 Thermal conductivity of Cf/LAS-SC1

Fig. 10 Mechanical properties of Cf/LAS-SC (a) Curves of temperature-bending strength relationship; (b) Curves of temperature-maximum displacement relationship; (c) Curve of temperature-elastic modulus relationship for Cf/LAS-SC1

参考文献 34

[1]	YE Z M, ZENG Y, XIONG X, et al. Elucidating the role of preferential oxidation during ablation: insights on the design and optimization of multicomponent ultra-high temperature ceramics. Journal of Advanced Ceramics, 2022, 11(12): 1956.
[2]	LYU Y, HAN Z H, ZHAO G D, et al. Efficient fabrication of light C_f/SiHfBOC composites with excellent thermal shock resistance and ultra-high-temperature ablation up to 1800 ℃. Journal of Advanced Ceramics, 2023, 12(11): 2062.
[3]	FAN Q G, CUI H, YAN L S, et al. Ablation resistance properties of ultra-high temperature composites C/C-SiC-ZrB₂ by slurry impregnation method. Journal of Inorganic Materials, 2013, 28(9): 1014.
[4]	KUMAR C V, KANDASUBRAMANIAN B. Advances in ablative composites of carbon based materials: a review. Industrial & Engineering Chemistry Research, 2019, 58(51): 22663.
[5]	XU L, LI X C, NI L Y, et al. Ablation behavior of functional gradient ceramic coating for porous carbon-bonded carbon fiber composites. Corrosion Science, 2018, 142: 145.
[6]	XU X T, PAN X H, NIU Y R, et al. Difference evaluation on ablation behaviors of ZrC-based and ZrB₂-based UHTCs coatings. Corrosion Science, 2021, 180: 109181.
[7]	SUI H, ZHANG H, GAO L F, et al. Boron and nitrogen doping in fused silica ceramics: structural, high-temperature mechanical and long-term ablation resistance properties of Si-B-O-N ceramics. Silicon, 2024, 16(12): 5147.
[8]	QUINTAL C C, CORMONT P, GALLAIS L. Experimental and numerical investigation of CO₂ laser ablation of fused silica with sub- microsecond pulses. Journal of Applied Physics, 2021, 130(9): 093106.
[9]	FARHAN S, WANG R M, LI K Z, et al. Sublimation and oxidation zone ablation behavior of carbon/carbon composites. Ceramics International, 2015, 41(10): 13751.
[10]	ZHANG W Z, TAN M Y, CHEN D M, et al. Sugar-derived nanocrystalline graphite matrix C/C composites with excellent ablative resistance at 3000 ℃. Advanced Materials, 2024, 36(7): 2309899.
[11]	CHENG L F, XU Y D, ZHANG L T, et al. Oxidation behavior of carbon-carbon composites with a three-layer coating from room temperature to 1700 ℃. Carbon, 1999, 37(6): 977.
[12]	FERREIRA J R, COPPINI N L, NETO F L. Characteristics of carbon-carbon composite turning. Journal of Materials Processing Technology, 2001, 109(1/2): 65.
[13]	HAN X, ZHANG S Y, LI W, et al. Preparation and thermal conductivity of C/C composites filled with diamond particles. Diamond and Related Materials, 2018, 88: 85.
[14]	WANG P P, LI H J, JIA Y J, et al. Ablation resistance of HfB₂-SiC coating prepared by in-situ reaction method for SiC coated C/C composites. Ceramics International, 2017, 43(15): 12005.
[15]	ZHAO J J, CAI R, MA Z K, et al. Preparation and properties of C/SiC composites reinforced by high thermal conductivity graphite films. Diamond and Related Materials, 2021, 116: 108376.
[16]	HE Z J, LI C, YANG B, et al. Interfacial reaction and brazing behaviour of SiC_f/SiC with C_f/C composites using Si-10Zr alloy at high temperatures. Journal of the European Ceramic Society, 2021, 41(2): 1142.
[17]	ZOU C R, LI B, MENG X J, et al. Ablation behavior and mechanism of SiO_2f/SiO₂, SiO_2f/BN and Si₃N_4f/BN radar wave transparent composites. Corrosion Science, 2018, 139: 243.
[18]	ZHOU G H, WANG S W, HUANG X X, et al. Unidirectional carbon fiber and SiC particulate co-reinforced fused silica composite. Ceramics International, 2007, 33(7): 1395.
[19]	VENKATESWARAN C, SREEMOOLANADHAN H, VAISH R. Lithium aluminosilicate (LAS) glass-ceramics: a review of recent progress. International Materials Reviews, 2022, 67(6): 620.
[20]	CHEN F, XU X R, XIA W W, et al. Practical nucleator agents for lithium aluminum silicate glass-ceramics. Glass, 2023, 50(11): 32.
[21]	ZHANG Y Y, ZHANG X M, GUO L X, et al. Effect of temperature-dependent nano SiC on the ablation resistance of ZrC coating. Journal of the European Ceramic Society, 2024, 44(12): 6875.
[22]	SCHERER G. W. Sintering of low-density glasses: I, theory. Journal of the American Ceramic Society, 1977, 60(5/6): 236.
[23]	YANG X, SU X L, YAN Y G, et al. Structures and thermoelectric properties of (GeTe)_nBi₂Te₃. Journal of Inorganic Materials, 2021, 36(1): 75.
[24]	LI T, ZHANG Y L, ZHANG J, et al. Improved antioxidative and mechanical properties of SiC coated C/C composites via a SiO₂-SiC reticulated layer. Journal of the European Ceramic Society, 2021, 41(13): 6151.
[25]	XIE W Q, ZHANG B, GE B Z, et al. Exceptionally low ablation rates realized in the cellular-structured MCMB@WC composites via biomimetic design. Composites Part A: Applied Science and Manufacturing, 2024, 179: 108035.
[26]	YUAN X B, LI R, XIONG Z, et al. Synergistic crystallization modulation and defects passivation via additive engineering stabilize perovskite films for efficient solar cells. Advanced Functional Materials, 2023, 33(24): 2215096.
[27]	DING Y S, DONG S M, HUANG Z R, et al. Fabrication of short C fiber-reinforced SiC composites by spark plasma sintering. Ceramics International, 2007, 33(1): 101.
[28]	ZAMAN W, LI K Z, IKRAM S, et al. Residual compressive and thermophysical properties of 4D carbon/carbon composites after repeated ablation under oxyacetylene flame of 3000 ℃. Transactions of Nonferrous Metals Society of China, 2013, 23(6): 1661.
[29]	YIN J, XIONG X, ZHANG H B, et al. Microstructure and ablation performances of dual-matrix carbon/carbon composites. Carbon, 2006, 44(9): 1690.
[30]	SHEN X T, SHI Z Q, ZHAO Z G, et al. Study of the ablation of a carbon/carbon composite at -25 MW/m² with a nitrogen plasma torch. Journal of the European Ceramic Society, 2020, 40(15): 5085.
[31]	YIN J, ZHANG H B, XIONG X, et al. Ablation properties of C/C-SiC composites tested on an arc heater. Solid State Sciences, 2011, 13(11): 2055.
[32]	ZHOU W X, CHENG Y, CHEN K Q, et al. Thermal conductivity of amorphous materials. Advanced Functional Materials, 2020, 30(8): 1903829.
[33]	TAKAMORI T, ROY R. Rapid crystallization of SiO₂-Al₂O₃ glasses. Journal of the American Ceramic Society, 1973, 56(12): 639.
[34]	SKORODUMOVA O B, SEMCHENKO G D, GONCHARENKO Y N, et al. Crystallization of SiO₂ from ethylsilicate-based gels. Glass and ceramics, 2001, 58: 31.

SiC_p掺杂C_f/Li₂O-Al₂O₃-SiO₂复合材料耐烧蚀性能研究

Ablative Properties of SiC_p Doped C_f/Li₂O-Al₂O₃-SiO₂ Composites

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