硅酸盐学报

掺杂纳米Ti对SiBCN陶瓷结构和电磁性能的影响

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陈平安 ¹^,² , 宗文丹 ¹^,² , 朱颖丽 ¹^,² , 陈浮 ²^,³ , 乔梦珂 ¹^,² , 吴江 ¹^,² , 李享成 ¹^,²

硅酸盐学报 | 第15届无机非金属材料专题研讨会专题(一)——研究论文 2026,54(4): 1177-1189

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硅酸盐学报 | 第15届无机非金属材料专题研讨会专题(一)——研究论文 2026, 54(4): 1177-1189

掺杂纳米Ti对SiBCN陶瓷结构和电磁性能的影响

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陈平安¹^,², 宗文丹¹^,², 朱颖丽¹^,², 陈浮²^,³, 乔梦珂¹^,², 吴江¹^,², 李享成¹^,²

作者信息

^1．武汉科技大学先进耐火材料全国重点实验室，武汉 430081

^2．武汉科技大学，高温电磁材料与结构教育部重点实验室，武汉 430081

^3．武汉科技大学信息科学与工程学院，武汉 430081

陈平安（1986—），男，博士，教授。

CHEN Pingan (1986-), male, Ph.D., Professor. E-mail: pinganchen@wust.edu.cn

通讯作者:

李享成（1978—），男，博士，教授。

Influence of Doped Ti Nanoparticles on Structure and Electromagnetic Properties of SiBCN Ceramics

Pingan CHEN¹^,², Wendan ZONG¹^,², Yingli ZHU¹^,², Fu CHEN²^,³, Mengke QIAO¹^,², Jiang WU¹^,², Xiangcheng LI¹^,²

Affiliations

^1.State Key Laboratory of Advanced Refractories, Wuhan University of Science and Technology, Wuhan 430081, China

^2.Key Laboratory of High Temperature Electromagnetic Materials and Structure of MOE, Wuhan University of Science and Technology, Wuhan 430081, China

^3.School of Information Science and Engineering, Wuhan University of Science and Technology, Wuhan 430081, China

出版时间: 2026-01-28 doi: 10.14062/j.issn.0454-5648.20250454

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摘要

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硅硼碳氮陶瓷（SiBCN）具有优异的抗氧化性能，在高温吸波材料领域具有广泛的应用前景。然而，纯SiBCN陶瓷中介电损耗相较少，导致其对电磁波的衰减能力较弱。为使SiBCN陶瓷能够在低温热处理后具有较好的电磁波吸收性能，本工作提出了一种简单的方法调控SiBCN的物相和显微结构以增强陶瓷对电磁波的吸收性能。实验结果表明，通过在SiBCN前驱体中掺杂纳米Ti粉，使SiBCN陶瓷在1000 ℃热处理后形成多孔结构并生成TiC、碳纳米管和晶体碳等介电损耗相，提高了陶瓷对电磁波的衰减能力。当掺杂质量分数为10%纳米Ti时，SiBCN陶瓷在频率为6.24 GHz时实现了最低反射损耗为-44.5 dB，有效衰减带宽达到了3.43 GHz。这项研究为低温制备SiBCN陶瓷电磁波吸收材料提供了一种简便可行的方法。

关键词

硅硼碳氮陶瓷 / 纳米钛掺杂 / 低温结晶 / 介电性能

Abstract

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Introduction

Polymer-derived ceramics are prepared via forming precursors through the polymerization of tiny molecules and cracking at high temperatures. Compared to conventional ceramics, their advantage lies in an ability to precisely control the microstructure and crystalline phase composition through the design of the molecular structure and elemental composition of the precursor and subsequent thermal treatment, thereby producing the optimal final properties. Among these, SiBCN ceramics stand out within the polymer-derived ceramics due to their flexible molecular structure designability. This enables the in-situ formation of multi-phase synergistic loss systems incorporating SiC, BN and graphitic carbon, coupled with a unique oxidation resistance mechanism, which excel particularly within polymer-derived ceramic systems. However, SiBCN ceramics primarily exist in an amorphous state at lower temperatures (i.e., < 1400 ℃), thus limiting their application in electromagnetic wave absorption. The paper was to introduce Ti nanopowder during the ceramicization process to catalyze the formation of nano-dielectric crystals such as SiC, TiC, and crystalline graphite. These crystals could enhance the dielectric imaginary part of SiBCN ceramics, thereby strengthening their electromagnetic wave attenuation capabilities.

Methods

For the synthesis of polymer precursor, tetrahydrofuran (THF)-methylvinyl dichlorosilane and borane dimethyl sulfide complex were mixed into a three-neck flask and conducted in argon for 24 h. Also, methyl dichlorosilane and hexamethyldisilazane were introduced, and the reaction was continued at the ambient temperature for 24 h. Subsequently, the mixture was then heated from room temperature to 170 ℃ for amide copolymerization reaction. After holding at this temperature for 3 h, vacuum distillation was performed, and filtrated for three cycles, thus producing a pale yellow polyborosilazane (PBSZ). For the synthesis of SiBCN ceramibs, polyborosilazane (PBSZ) was placed in a tube furnace and heated to 280 ℃ for 2 h to fully cure the precursor. The cured sample was subjected to ball grinding. The resultant ground powder was mixed with Ti nanopowder at different Ti mass contents (i.e, 0%, 5%, 10%, and 15%), and then was ground to produce different composite powders, . The composite powders were pressed into discs with the diameter of φ20 mm. The discs were heat-treated in a vertical tube furnace(i.e., firstly heating at 800 ℃ for 1 h, and thenheating at 1000 ℃ for 2 h) to allow enough molecular diffusion for TiC crystal formation, resulting in SiBCN ceramics.

Results and discussion

The analysis of the four-component doped ceramics reveals that Ti nanoparticles doping positively affects both the phase composition and dielectric properties of SiBCN ceramics. The XRD patterns indicate that pure SiBCN ceramics remain amorphous after heat treatment at 1000 ℃, whereas the addition of Ti nano-particles promotes the formation of TiC crystals within the ceramics, thereby enhancing their crystalline properties. The SEM and TEM images demonstrate that varying the nano-Ti doping content alters the microstructure of SiBCN ceramics. Nano-Ti addition promotes the formation of a porous structure within the ceramics and facilitates the growth of crystals such as TiC and carbon nanotubes, enriching the phase composition of the ceramics. Varying Ti nanoparticles doping contents alters SiBCN's electromagnetic wave absorption and loss capabilities. Compared to pure SiBCN ceramics, Ti nanoparticles doping confers higher electromagnetic parameters and lower reflection loss, and 10% Ti nanoparticles-doped SiBCN exhibits the optimum electromagnetic wave absorption performance. The incorporation of Ti nanoparticles optimizes the ceramic structure, with synergistic interactions among various crystals and structural components, thus enhancing the overall performance.

Conclusions

This study demonstrated that doping Ti nano-particles into SiBCN ceramic could enhance the ceramic dielectric loss and impedance matching qualities. Ti nano-particles enhanced the low-temperature crystallization property of SiBCN. The crystallinity and microstructure of SiBCN ceramics could be adjusted by varying the nano-Ti doping content. The ceramics heat-treated at 1000 ℃ could develop porous architectures, TiC, and crystalline phases such as crystalline carbon. Ti nanoparticles improved the electromagnetic wave attenuation properties of SiBCN. The formation of TiC and carbon nanotubes, along with the heterogeneous interfaces formed with the amorphous matrix, could boost the electromagnetic wave attenuation performance of SiBCN ceramics. The crystallinity of SiBCN ceramics and the presence of abundant atomic defects resulted in a significant polarization loss, thereby enhancing the ceramic's electromagnetic wave absorption capability. At Ti nanoparticles content of 10%, the RLmin value of SiBCN ceramics at 6.24 GHz achieved -44.5 dB, with an EAB as high as 3.43 GHz, indicating that adding Ti nanoparticles could effectively enhance the electromagnetic wave absorption capacity of low-temperature heat-treated SiBCN ceramics.

Key words

silicon-boron-carbon-nitride ceramics / nano-titatium doped / low-temperature crystallization / electromagnetic performance

引用本文

陈平安, 宗文丹, 朱颖丽, 陈浮, 乔梦珂, 吴江, 李享成. 掺杂纳米Ti对SiBCN陶瓷结构和电磁性能的影响. 硅酸盐学报, 2026 , 54 (4) : 1177 -1189 . DOI: 10.14062/j.issn.0454-5648.20250454

Pingan CHEN, Wendan ZONG, Yingli ZHU, Fu CHEN, Mengke QIAO, Jiang WU, Xiangcheng LI. Influence of Doped Ti Nanoparticles on Structure and Electromagnetic Properties of SiBCN Ceramics[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (4) : 1177 -1189 . DOI: 10.14062/j.issn.0454-5648.20250454

基金

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国家重点研发计划项目(2024YFB3714600)
国家自然科学基金项目(U2541259; 52304410)
湖北省重大项目(功能性涂层材料; 2023BAA003)
湖北省创新研究群体项目(JCZRQT202600033)

参考文献

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2026年第54卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250454

接收时间：2025-06-10
首发时间：2026-05-20
出版时间：2026-01-28

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收稿日期：2025-06-10
修回日期：2025-09-29

基金

国家重点研发计划项目(2024YFB3714600)

国家自然科学基金项目(U2541259; 52304410)

湖北省重大项目(功能性涂层材料; 2023BAA003)

湖北省创新研究群体项目(JCZRQT202600033)

作者信息

^1．武汉科技大学先进耐火材料全国重点实验室，武汉 430081

^2．武汉科技大学，高温电磁材料与结构教育部重点实验室，武汉 430081

^3．武汉科技大学信息科学与工程学院，武汉 430081

通讯作者:

李享成（1978—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250454

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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