硼酸碳热还原-渗硅反应烧结制备碳化硼陶瓷复合材料

doi:10.15541/jim20230588

无机材料学报 ›› 2024, Vol. 39 ›› Issue (6): 707-714.DOI: 10.15541/jim20230588

硼酸碳热还原-渗硅反应烧结制备碳化硼陶瓷复合材料

郑雅雯(), 张翠萍(), 张瑞杰, 夏乾, 茹红强

东北大学材料科学与工程学院, 材料各向异性与织构教育部重点实验室, 沈阳 110819

收稿日期:2023-12-21 修回日期:2024-03-17 出版日期:2024-06-20 网络出版日期:2024-03-22
通讯作者: 张翠萍, 讲师. E-mail: zhangcp@smm.neu.edu.cn
作者简介:郑雅雯(2000-), 女, 硕士研究生. E-mail: zheng_ya_wen@163.com
基金资助:
辽宁省教育厅基本科研面上项目(LJKMZ20220340);公安部科技计划(2022ZB03)

Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering

ZHENG Yawen(), ZHANG Cuiping(), ZHANG Ruijie, XIA Qian, RU Hongqiang

Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education, School of Materials Science and Engineering, Northeastern University, Shenyang 110819, China

Received:2023-12-21 Revised:2024-03-17 Published:2024-06-20 Online:2024-03-22
Contact: ZHANG Cuiping, lecturer. E-mail: zhangcp@smm.neu.edu.cn
About author:ZHENG Yawen (2000-), female, Master candidate. E-mail: zheng_ya_wen@163.com
Supported by:
Expenses of Basic Scientific Research Project of Liaoning Province(LJKMZ20220340);Science and Technology Plan of the Ministry of Public Security(2022ZB03)

摘要/Abstract

摘要：

碳化硼性能优良, 应用广泛, 但制备成本较高。为了从源头解决碳化硼陶瓷材料制备成本高的问题, 本工作直接以碳热还原法合成的碳化硼-C复合粉体为原料, 无需进行破碎提纯, 通过渗硅反应烧结制备碳化硼复合材料, 所得材料性能与以市售碳化硼粉体为原料制备的材料性能相当, 有效降低了其制备成本。主要研究了原料碳硼摩尔比对合成粉体以及碳化硼复合材料物相、显微组织和性能的影响, 并探讨了碳化硼陶瓷复合材料的强韧化机理。结果表明: 随着碳硼摩尔比增加, 合成粉体中碳化硼粉体的碳硼原子比增加, 且合成粉体中游离C含量增加; 当碳硼摩尔比为2.01时, 游离C包覆在碳化硼粉体颗粒表面。复合材料相组成均为B₁₂(C,Si,B)₃、SiC和Si, 随着碳硼摩尔比的增加, 复合材料中碳化硼和游离Si含量降低, SiC含量、大尺寸SiC区域的尺寸、大尺寸SiC区域和纳米SiC颗粒的数量均增加。大尺寸SiC区域的产生会降低材料的强度和韧性, 而SiC纳米颗粒的形成有利于提高材料的强度和韧性。当碳硼摩尔比为1.35时, 复合材料的抗弯强度和断裂韧性最高, 分别为338 MPa和4.06 MPa∙m^1/2。

关键词: 碳化硼, 碳热还原法, 渗硅反应烧结, 碳硼摩尔比, 显微组织

Abstract:

Boron carbide possesses excellent properties and has a wide range of applications, but its production cost is relatively high. To address this issue, boron carbide-C composite powder was directly used, synthesized by carbothermal reduction method, as the raw material without any crushing and purification. Boron carbide composites were prepared through silicon infiltration reaction sintering, yielding material properties comparable to those prepared from commercially available boron carbide powder, which effectively reduced its preparation cost. This study mainly investigated the influence of the molar ratio of carbon to boron in the synthesis of powder on the phase composition, microstructure and properties of boron carbide ceramic composite materials, and explored the toughening mechanism of boron carbide ceramic composites. With the increase of the molar ratio of carbon to boron, the atomic ratio of carbon to boron in the synthesized boron carbide powder increases, as well as the content of free C, which coats the surface of the boron carbide particles at the molar ratio of 2.01. The phase composition of the boron carbide composite materials is B₁₂(C,Si,B)₃, SiC and Si. With the increase of carbon-boron molar ratio, the content of boron carbide and free Si in the composite decrease, while the content of SiC, the size of large SiC region, and the number of large SiC regions and SiC nanoparticles increase. Formation of large SiC regions decreases the strength and toughness of the material, while creation of SiC nanoparticles contributes to improvement of strength and toughness. When the carbon to boron molar ratio is 1.35, the composite exhibits the highest flexural strength and fracture toughness, reaching 338 MPa and 4.06 MPa∙m^1/2, respectively.

Key words: boron carbide, carbothermal reduction method, silicon infiltration reaction sintering, molar ratio of carbon to boron, microstructure

中图分类号:

TQ174

郑雅雯, 张翠萍, 张瑞杰, 夏乾, 茹红强. 硼酸碳热还原-渗硅反应烧结制备碳化硼陶瓷复合材料[J]. 无机材料学报, 2024, 39(6): 707-714.

ZHENG Yawen, ZHANG Cuiping, ZHANG Ruijie, XIA Qian, RU Hongqiang. Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering[J]. Journal of Inorganic Materials, 2024, 39(6): 707-714.

图/表 9

图1 不同nC/nB条件下合成的粉体的XRD图谱

Fig. 1 XRD patterns of synthesized powders under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

图2 不同nC/nB条件下合成粉体的SEM二次电子照片

Fig. 2 SEM secondary electron images of synthesized powders under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

图3 不同nC/nB条件下制备的B4C复合材料的XRD图谱

Fig. 3 XRD patterns of B4C composite materials prepared under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

图4 不同nC/nB条件下B4C复合材料的SEM背散射照片

Fig. 4 SEM backscatter images of B4C composite materials prepared under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

表1 不同nC/nB条件下B4C复合材料各相的体积分数与SiC相尺寸

Table 1 Volume fraction of B4C composite materials and phase size of SiC under different nC/nB conditions

n_C/n_B	Volume fraction/%			D_mean/μm
n_C/n_B	B₁₂(B,C,Si)₃	SiC	Si	SiC
1.35	57.21	19.47	23.32	5.32
1.75	56.71	24.68	18.61	5.59
1.93	52.57	36.24	11.18	6.18
2.01	51.98	38.07	9.95	5.99

图5 不同nC/nB条件下B4C复合材料的SEM二次电子照片

Fig. 5 SEM secondary electron images of B4C composite materials prepared under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

图6 不同nC/nB条件下B4C复合材料的体积密度和开口气孔率

Fig. 6 Volume density and open porosity of B4C composite materials under different nC/nB conditions

图7 不同nC/nB条件下B4C复合材料的力学性能

Fig. 7 Mechanical properties of boron carbide composite materials under different nC/nB conditions (a) Vickers hardness; (b) Bending strength; (c) Fracture toughness

图8 nC/nB=2.01的碳化硼复合材料的压痕裂纹扩展照片

Fig. 8 Indentation crack propagation images of boron carbide composite material obtained at nC/nB=2.01 (a, b) Crack deflection; (c) Particle pullout

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硼酸碳热还原-渗硅反应烧结制备碳化硼陶瓷复合材料

Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering

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