含有石墨烯阵列的SiC基陶瓷材料的制备与力学性能

doi:10.15541/jim20230259

无机材料学报 ›› 2024, Vol. 39 ›› Issue (3): 267-273.DOI: 10.15541/jim20230259 CSTR: 32189.14.10.15541/jim20230259

所属专题：【结构材料】陶瓷基复合材料(202512)；【信息功能】MAX、MXene及其他二维材料(202512)

含有石墨烯阵列的SiC基陶瓷材料的制备与力学性能

孙川¹(), 何鹏飞¹, 胡振峰¹, 王荣¹, 邢悦¹, 张志彬¹, 李竞龙¹, 万春磊², 梁秀兵¹()

1.军事科学院国防科技创新研究院, 北京 100071
2.清华大学新型陶瓷与精细工艺国家重点实验室, 北京 100084

收稿日期:2023-06-02 修回日期:2023-07-28 出版日期:2024-03-20 网络出版日期:2023-08-31
通讯作者: 梁秀兵, 研究员. E-mail: liangxb_d@163.com
作者简介:孙川(1986-), 男, 博士. E-mail: sunchuanyeah@163.com
基金资助:
国家自然科学基金(51975582);北京市科技计划课题(Z211100002421003)

SiC-based Ceramic Materials Incorporating GNPs Array: Preparation and Mechanical Characterization

SUN Chuan¹(), HE Pengfei¹, HU Zhenfeng¹, WANG Rong¹, XING Yue¹, ZHANG Zhibin¹, LI Jinglong¹, WAN Chunlei², LIANG Xiubing¹()

1. National Innovation Institute of Defense Technology, Academy of Military Sciences of the People’s Liberation Army of China, Beijing 100071, China
2. State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, China

Received:2023-06-02 Revised:2023-07-28 Published:2024-03-20 Online:2023-08-31
Contact: LIANG Xiubing, professor. E-mail: liangxb_d@163.com
About author:SUN Chuan (1986-), male, PhD. E-mail: sunchuanyeah@163.com
Supported by:
National Natural Science Foundation of China(51975582);Beijing Municipal Science and Technology Project(Z211100002421003)

摘要/Abstract

摘要：

碳化硅陶瓷是一种重要工程材料, 但具有一定的脆性, 这限制了其进一步应用。二维石墨烯具有诸多优良特性, 可以作为第二相对碳化硅陶瓷材料进行性能改善。然而石墨烯在陶瓷基体中存在分散性较差等问题, 难以发挥其对陶瓷基体的改性作用。为解决以上问题, 本工作以陶瓷有机前驱体聚碳硅烷和工业可膨胀石墨为原料, 通过前驱体-纳米插层技术制备了少层石墨烯纳米片(GNPs)的体积分数分别为1%、3%和5%的SiC/GNPs陶瓷基复合材料。GNPs在SiC陶瓷基体中呈阵列态平行排布, 显示出极高的取向性; 随着GNPs含量增加, 阵列中GNPs的间距依次递减, 表现出一定的微观组织拓扑可调节性; 加入GNPs显著提高了SiC陶瓷的断裂韧性, 当GNPs含量为3%时, 样品的相对密度为98.5%, 抗弯强度为445 MPa, 断裂韧性达到最高值5.67 MPa·m^1/2, 相比纯SiC陶瓷提高了40%, 由GNPs引发的裂纹偏转与桥连是主要的增韧机制。而进一步提高GNPs含量, 断裂韧性下降至4.37 MPa·m^1/2。这种含有石墨烯阵列的复合材料可以用于新型“结构-功能一体化”SiC基陶瓷器件的设计与开发。

关键词: 碳化硅, 石墨烯, 微观组织, 断裂韧性, 陶瓷增韧

Abstract:

Silicon carbide ceramics are important engineering materials, but their application is limited by the inherent brittleness. Two-dimensional graphene, with its excellent properties, can be used as a second phase to improve the performance of silicon carbide ceramics. However, due to poor dispersion of graphene in the ceramic matrix, it is a challenge to fully exploit the modifying effect of graphene in composite materials. To address these challenges, SiC-based ceramic materials incorporating graphene nanosheets (GNPs) were synthesized using ceramic organic precursor polycarbosilane and industrial expandable graphite as starting materials. The precursor intercalation technique was employed to fabricate SiC/GNPs ceramic composites with GNPs volume fraction of 1%, 3%, and 5%. The GNPs were uniformly arranged in an array-like parallel fashion in the SiC ceramic matrix, showing excellent orientation. With the GNPs content increasing, the spacing between GNPs within the array decreased, indicating tunable microstructural topology. The addition of GNPs greatly enhanced the fracture toughness of SiC ceramics. When the GNPs content was 3%, the relative density of the samples reached 98.5%, the bending strength reached 445 MPa, and the fracture toughness (K_IC value) peaked at 5.67 MPa·m^1/2, surpassing pure SiC ceramics by 40%, which was primarily attributed to crack deflection and bridging induced by the GNPs. However, further increase in GNPs content led to a decrease in fracture toughness to 4.37 MPa·m^1/2. These SiC-based ceramic composites with a graphene array have potential application in design and development of novel “structure-function integration” SiC-based ceramic devices.

Key words: silicon carbide, graphene, microstructure, fracture toughness, ceramic toughening

中图分类号:

TQ174

孙川, 何鹏飞, 胡振峰, 王荣, 邢悦, 张志彬, 李竞龙, 万春磊, 梁秀兵. 含有石墨烯阵列的SiC基陶瓷材料的制备与力学性能[J]. 无机材料学报, 2024, 39(3): 267-273.

SUN Chuan, HE Pengfei, HU Zhenfeng, WANG Rong, XING Yue, ZHANG Zhibin, LI Jinglong, WAN Chunlei, LIANG Xiubing. SiC-based Ceramic Materials Incorporating GNPs Array: Preparation and Mechanical Characterization[J]. Journal of Inorganic Materials, 2024, 39(3): 267-273.

图/表 8

图1 SiC/GNPs复合材料的制备过程示意图

Fig. 1 Facile route to synthesize the SiC/GNPs composite

表1 SiC/GNPs复合材料的基本物性

Table 1 Basic physical properties of SiC/GNPs composites

No.	GNPs content/(%, in vol)	Relative density/%	GNPs average layer spacing/μm	K_IC/(MPa·m^1/2)	Bending strength/MPa
G0	0	99.2	-	4.05	395
G1	~1	99.0	7.5	5.18	410
G3	~3	98.5	5.2	5.67	445
G5	~5	97.4	3.4	4.37	370

图2 微波加热后得到的膨胀石墨的SEM照片

Fig. 2 SEM image of the expanded graphite prepared after the microwave management

图3 SiC/GNPs混合粉体SEM照片

Fig. 3 SEM image of the SiC/GNPs mixed powder

图4 SiC/GNPs复合材料的显微组织形貌

Fig. 4 SEM and TEM images of the fractured surface of SiC/GNPs bulks (a) SEM image of sample G1; (b) SEM image of sample G3; (c) SEM image of sample G5; (d) TEM image of GNP in SiC matrix

图5 SiC/GNPs混合粉体和烧结体的XRD图谱

Fig. 5 XRD patterns of SiC/GNPs mixed powder and bulks

图6 G3样品混合粉体与烧结块体的拉曼光谱图

Fig. 6 Raman spectra of G3 mixed powder and bulk

图7 SiC/GNPs复合材料的断裂性能

Fig. 7 Fracture properties of SiC/GNPs sample (a) Changing curves of fracture toughness and bending strength of SiC/GNPs with GNPs content; (b) SEM image of sample showing crack bridging; (c) SEM image of sample showing crack deflection

参考文献 40

[1]	ZABELINA A A, SHCHERBAKOVA G I, FAIKOV P P, et al. SiC composites containing carbon nanotubes and oxide additives based on organoelementoxanes. Preparation by spark plasma sintering. Ceramics International, 2020, 46(3): 2786. DOI URL
[2]	OUYANG Q, WANG Y F, XU J, et al. Research progress of SiC fiber reinforced SiC composites for nuclear application. Journal of Inorganic Materials, 2022, 37(8): 821. DOI
[3]	KOYANAGI T, KATOH Y, NOZAWA T, et al. Recent progress in the development of SiC composites for nuclear fusion applications. Journal of Nuclear Materials, 2018, 511(1): 544. DOI URL
[4]	YAO X Y, LI K Z, REN J J, et al. Microstructure and fatigue behavior of high texture three-dimensional C/C composites prepared by mixed precursors. Journal of Inorganic Materials, 2020, 35(5): 589. DOI
[5]	李辰冉, 谢志鹏, 赵林. 碳化硅陶瓷材料烧结技术的研究与应用进展. 陶瓷学报, 2020, 41(2): 13.
[6]	LIAO L, CHEN Z, XU X H, et al. Effects of oxidation curing and sintering temperature on the microstructure formation and heat transfer performance of freestanding polymer-derived SiC films for high-power LEDs. Ceramics International, 2018, 44(6): 6072. DOI URL
[7]	乔玉林, 薛胤昌, 刘军, 等. 聚合物先驱体材料体系的陶瓷化研究进展与展望. 材料导报, 2016, 30(11): 6.
[8]	BALANDIN A A, GHOSH S, BAO W, et al. Superior thermal conductivity of single-layer graphene. Nano Letters, 2008, 8(3): 902. DOI PMID
[9]	BOLOTIN K I, SIKES K J, JIANG Z, et al. Ultrahigh electron mobility in suspended graphene. Solid State Communications, 2008, 146(9/10): 351. DOI URL
[10]	CHAE H K, SIBERIO-PÉREZ D Y, KIM J, et al. A route to high surface area, porosity and inclusion of large molecules in crystals. Nature, 2004, 427(6974): 523. DOI
[11]	MULLER S E, SANTHAPURAM R R, NAIR A K. Failure mechanisms in pre-cracked Ni-graphene nanocomposites. Computational Materials Science, 2018, 152: 341. DOI URL
[12]	LEE C, WEI X, KYSAR J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science, 2008, 321(5887): 385. DOI PMID
[13]	WANG Y, HUANG Y, SONG Y, et al. Room-temperature ferromagnetism of graphene. Nano Letters, 2009, 9(1): 220. DOI PMID
[14]	HAN T, HE P, WANG J, et al. The effect of vacancy defects on the tensile mechanical properties of single graphene sheets. Journal of Tongji University (Natural Science), 2010, 38(8): 1210.
[15]	ZHANG B, HOU C Y, WANG H P, et al. Preparation and performance of reduced graphene oxide functionalized flexible and multicolor electrothermal chromatic films. Journal of Inorganic Materials, 2018, 33(11): 1232. DOI
[16]	YU Y, XIA F, HUANG Q, et al. Electrical conductivity of silicon carbonitride-reduced graphene oxide composites. Journal of the American Ceramic Society, 2017, 100(11): 5113. DOI URL
[17]	LEE B, KOO M Y, JIN S H, et al. Simultaneous strengthening and toughening of reduced graphene oxide/alumina composites fabricated by molecular-level mixing process. Carbon, 2014, 78: 212. DOI URL
[18]	SUN C, HUANG Y, SHEN Q, et al. Embedding two-dimensional graphene array in ceramic matrix. Science Advances, 2020, 6(39): eabb1338. DOI URL
[19]	FAN Y, WANG L, LI J, et al. Preparation and electrical properties of graphene nanosheet/Al₂O₃ composites. Materials Science, 2010, 48(6): 1743.
[20]	FAN Y, SONG Y, TUFAIL, et al. Liquid-phase assisted engineering of highly strong SiC composite reinforced by multiwalled carbon nanotubes. Advanced Science, 2020, 7(21): 2002225 DOI URL
[21]	GAO J, DING Q, YAN P, et al. Highly improved microwave absorbing and mechanical properties in cold sintered ZnO by incorporating graphene oxide. Journal of the European Ceramic Society, 2022, 42(3): 993. DOI URL
[22]	YANG Y F, ZHU T B, DAN J N, et al. Mechanical and tribological properties of SiC-GNPs composites prepared by oscillatory pressure sintering. Ceramics International, 2022, 48(23): 34769. DOI URL
[23]	HANZEL O, TATARKO P. Preparation and properties of layered SiC-graphene composites for EDM. Materials, 2021, 14(11): 2916. DOI URL
[24]	HUANG Y H, JIANG D L, CHEN Z M, et al. Fabrication and property of rGO/SiC composite. Journal of Inorganic Materials, 2018, 33(11): 1147. DOI URL
[25]	RAZMJOO A, BAHARVANDI H R, EHSANI N. αSiC-βSiC- graphene composites. Scientific Reports, 2023, 13: 4306. DOI
[26]	FAN Y C, WANG L J, JIANG W. Graphene based oxide ceramic composites with high mechanical and functional performance: from preparation to property. Journal of Inorganic Materials, 2018, 33(2): 138. DOI URL
[27]	TANG J, LIU M, WEI Y, et al. An efficient and low-cost liquid silicon infiltration method to prepare SiC-coated carbon short fiber for fiber protection of C_f/SiC ceramic matrix composites. Ceramics International, 2021, 47(9): 13235. DOI URL
[28]	LIN B, WEI J, SUI T, et al. Effects of the surface processing on the tribological performance of C/SiCs under dry friction. Scientific Reports, 2020, 10: 5990. DOI PMID
[29]	HU X, HUANG M, KONG N, et al. Enhancing the electrical insulation of highly thermally conductive carbon fiber powders by SiC ceramic coating for efficient thermal interface materials. Composites Part B Engineering, 2021, 227(2): 109398. DOI URL
[30]	WANG X, SONG Z, CHENG Z, et al. Tensile creep properties and damage mechanisms of 2D-SiC_f/SiC composites reinforced with low-oxygen high-carbon type SiC fiber. Journal of the European Ceramic Society, 2020, 40(14): 4872. DOI URL
[31]	邓卫斌, 李铁虎, 李昊, 等. 石墨烯/陶瓷复合材料的研究进展. 固体火箭技术, 2022, 45(1): 13.
[32]	侯保江, 水涌涛, 孙向春, 等. 碳化硅陶瓷超声波辅助磨削表面完整性研究. 兵器装备工程学报, 2019(7): 3.
[33]	徐广平, 何江荣, 刘鹏程, 等. 振荡压力烧结技术制备高性能碳化硅陶瓷. 中国陶瓷, 2022(3): 58.
[34]	YIN Z, ZHANG X, HUANG Z, et al. Paraffin/expanded graphite phase change composites with enhanced thermal conductivity prepared by implanted β-SiC nanowires with chemical vapor deposition method. Materials Research Express, 2018, 5(2): 25503. DOI URL
[35]	贺国旭, 曹测祥, 韩永军, 等. 反应烧结制备碳化硅陶瓷及其性能研究. 耐火材料, 2022(2): 056.
[36]	李红伟, 王瑶琪, 高莹, 等. 工业级石墨烯纳米片对碳化硅陶瓷摩擦磨损性能影响的研究. 中国陶瓷, 2021, 57(5): 7.
[37]	PAPAGEORGIOU D G, KINLOCH I A, YOUNG R J. Mechanical properties of graphene and graphene-based nanocomposites. Progress in Materials science. 2017, 90(10): 75. DOI URL
[38]	RAMIRE Z, VEGA-DIAZ S M, MORELOS-GÓMEZ A, et al. Synthesis of conducting graphene/Si₃N₄ composites by spark plasma sintering. Carbon, 2013, 57: 425. DOI URL
[39]	COLEMAN J N, LOTYA M, O'NEILL A, et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science, 2011, 331(6017): 568. DOI PMID
[40]	TAN Y, LUO H, ZHANG H, et al. Lightweight graphene nanoplatelet/boron carbide composite with high EMI shielding effectiveness. AIP Advances, 2016, 6(3): 35208. DOI URL

含有石墨烯阵列的SiC基陶瓷材料的制备与力学性能

SiC-based Ceramic Materials Incorporating GNPs Array: Preparation and Mechanical Characterization

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 40

相关文章 15

编辑推荐

Metrics

本文评价

[1]	刘雷敏, 罗红心, 何玉梅, 金利民, 李永杰, 刘静雯, 魏玉全, 孙安乐, 陈忠明, 刘学建, 殷杰, 黄政仁. 先进光源装置用碳化硅反射镜性能研究[J]. 无机材料学报, 2026, 41(6): 805-813.
[2]	孙丽, 徐永善, 高义华. 石墨烯/Bi₂O₂Se/石墨烯双异质结器件的光探测和仿生突触研究[J]. 无机材料学报, 2026, 41(6): 795-804.
[3]	汪加辉, 刘晶晶, 邱毅, 王永霞, 崔香枝. 原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能[J]. 无机材料学报, 2026, 41(6): 814-822.
[4]	秦英, 姚焯, 郑丽君, 包硕, 李鹏, 郭诗淇. 柔性超级电容器硫掺杂石墨烯/导电聚合物复合电极材料的制备及性能研究[J]. 无机材料学报, 2026, 41(5): 604-610.
[5]	程澳芃, 王跃文, 许文涛, 刘全伟, 张海涛, 周有福. 吸附-沉淀自组装结合放电等离子烧结法制备石墨烯增强氧化铝复合陶瓷[J]. 无机材料学报, 2026, 41(4): 536-544.
[6]	朱开煌, 杨世杰, 李欣格, 宋贯卿, 史淦升, 王焱, 任小孟, 陆遥, 徐新宏, 孙静. 基于UiO-66骨架的氧化石墨烯改性金属有机框架凝胶的制备及其对甲苯的高效吸附性能[J]. 无机材料学报, 2026, 41(4): 519-526.
[7]	蒋圣楠, 郑重, 何唯一, 刘涛, 潘秀红, 陈锟, 郭辉, 高攀, 刘春俊, 刘学超. 硼镓共掺氧化锌透明电极的制备及性能优化[J]. 无机材料学报, 2026, 41(4): 479-485.
[8]	曹娟, 吴西士, 刘泽华, 裴兵兵, 韩建燊, 刘欢, 杨亦天, 吴海波, 黄政仁. 晶粒尺寸对常压固相烧结SiC陶瓷断裂强度Weibull分布的影响[J]. 无机材料学报, 2026, 41(2): 217-224.
[9]	范雨竹, 王媛, 王林燕, 向美玲, 鄢雨婷, 黎本慧, 李敏, 文志东, 王海超, 陈永福, 邱会东, 赵波, 周成裕. 氧化石墨烯基吸附材料去除水体中Pb(II): 制备、性能及机理[J]. 无机材料学报, 2026, 41(1): 12-26.
[10]	王鲁杰, 张玉新, 李彤阳, 于源, 任鹏伟, 王建章, 汤华国, 姚秀敏, 黄毅华, 刘学建, 乔竹辉. 深海服役环境下碳化硅陶瓷材料的腐蚀及磨损行为[J]. 无机材料学报, 2025, 40(7): 799-807.
[11]	杨茗凯, 黄泽皑, 周芸霄, 刘彤, 张魁魁, 谭浩, 刘梦颖, 詹俊杰, 陈国星, 周莹. 基于Cu与金属氧化物-KCl熔融介质的甲烷热解制备少层石墨烯与氢气联产研究[J]. 无机材料学报, 2025, 40(5): 473-480.
[12]	李紫薇, 弓伟露, 崔海峰, 叶丽, 韩伟健, 赵彤. 前驱体法制备(Zr, Hf, Nb, Ta, W)C-SiC复相陶瓷及性能研究[J]. 无机材料学报, 2025, 40(3): 271-280.
[13]	高晨光, 孙晓亮, 陈君, 李达鑫, 陈庆庆, 贾德昌, 周玉. 基于湿法纺丝技术的SiBCN-rGO陶瓷纤维的组织结构、力学和吸波性能[J]. 无机材料学报, 2025, 40(3): 290-296.
[14]	王悦, 王欣, 于显利. 室温铁磁性还原氧化石墨烯基全碳膜[J]. 无机材料学报, 2025, 40(3): 305-313.
[15]	王浩, 刘学超, 郑重, 潘秀红, 徐锦涛, 朱新锋, 陈锟, 邓伟杰, 汤美波, 郭辉, 高攀. 非本征背照触发平面型4H-SiC光导开关性能研究[J]. 无机材料学报, 2024, 39(9): 1070-1076.