Article(id=1320107619126195108, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320107605469544753, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250803, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1762012800000, receivedDateStr=2025-11-02, revisedDate=1763740800000, revisedDateStr=2025-11-22, acceptedDate=null, acceptedDateStr=null, onlineDate=1792667782812, onlineDateStr=2026-10-22, pubDate=1786982400000, pubDateStr=2026-08-18, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792667782812, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792667782812, creator=13701087609, updateTime=1792667782812, updator=13701087609, issue=Issue{id=1320107605469544753, tenantId=1146029695717560320, journalId=1263187385517883426, year='2026', volume='54', issue='9', pageStart='2949', pageEnd='3314', issueExtLink='null', onlineDate='null', pubDate='1789833600000', pubDateStr='2026-09-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792667779556, creator='13701087609', updateTime=1792737576818, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320400356446687492, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320107605469544753, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320400356446687493, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320107605469544753, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3137, endPage=3149, ext={EN=ArticleExt(id=1320107619323327397, articleId=1320107619126195108, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Effect of Silicon Content on Microstructure and Electromagnetic Properties of SiBCN Polymer-Derived Ceramics, columnId=1263922769897599102, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Articles, runingTitle=null, highlight=null, articleAbstract=
Introduction

SiBCN polymer-derived ceramics (PDCs) are highly promising for high-temperature electromagnetic wave attenuation due to their unique "wave-transmitting/lossy" composite structure, which arises from the in-situ formation of high-dielectric crystals within a low-dielectric amorphous matrix. A critical challenge, however, lies in precisely tailoring their microstructure to maximize absorption performance. To address this issue, SiBCN ceramics were synthesized with different compositions via modulating the silicon (Si) content in the polymer precursors to elucidate the regulatory mechanisms governing phase composition, morphology, and electromagnetic absorption properties. The results reveal that high-temperature treatment induces the crystallization of Si3N4, SiC, and graphitic carbon. The incorporation of Si can facilitate the graphitization of amorphous carbon and effectively reduce internal defect density. Furthermore, an increase in Si content promotes the formation of the Si3N4 phase, thereby enhancing impedance matching. The optimized SiBCN ceramics demonstrate superior microwave absorption capabilities, achieving a minimum reflection loss of -54.38 dB at 13.49 GHz (2.28 mm thickness) and a broad effective absorption bandwidth of 6.61 GHz (2.24 mm thickness). Consequently, this study confirms that tuning the precursor Si content effectively optimizes both the structural configuration and impedance matching of SiBCN ceramics, offering a robust theoretical and experimental foundation for their application in high-temperature environments.

Methods

Under ice bath conditions, 20 g of n-hexane was added to a reaction flask, followed by the sequential addition of dimethyldichlorosilane, boron trichloride, borane dimethyl sulfide complex, and hexamethyldisilazane according to different molar ratios of the raw materials. The mixture was stirred in Ar atmosphere for 24 h. The temperature was then raised to 100 ℃ and maintained for 3 h to remove n-hexane and other by-products. Finally, the temperature increased to 160 ℃ and maintained for 3 h, followed by three cycles of vacuum filtration to obtain a pale yellow resin-like polyborosilazane. A series of polyborosilazanes with different silicon contents were prepared via varying the amount of dimethyldichlorosilane added. The samples with different dimethyldichlorosilane to hexamethyldisilazane molar ratios of 1∶6, 2∶6, and 4∶6 were designated as S30, S38, and S45, with silicon contents of 30%, 38%, and 45%, respectively.

The precursor samples (S30, S38, and S45) were first cured under an N2 atmosphere by heating to 280 ℃ at a rate of 2 ℃/min and holding for 2 h. The cured samples were subsequently heated to 1000 ℃ under an N2 atmosphere at a rate of 5 ℃/min and held for 1 h. They were then further heated to either 1400 or 1600 ℃ at a rate of 2 ℃/min and held for 2 h. The resulting ceramic samples were designated as S30-1400, S38-1400, S45-1400, S30-1600, S38-1600, and S45-1600, respectively.

Results and discussion

The phase composition, microstructure, and electromagnetic properties of the resulting ceramics are regulated via controlling the silicon content in the polymer precursor. The results indicate that after heat treatment in N2 atmosphere at 1600 ℃, crystals such as Si3N4, SiC, and graphitic carbon are formed within the SiBCN ceramics. Silicon promotes the transformation of amorphous carbon into crystalline carbon in the SiBCN ceramics, reduces the defect density within the ceramics, and enhances the graphitization degree. The formation of Si3N4 in the SiBCN ceramics increases with increasing silicon content, improving the impedance matching performance of the ceramics. When the thickness of the SiBCN ceramics is 2.28 mm, the minimum reflection loss reaches -54.38 dB at 13.49 GHz. At a thickness of 2.24 mm, the effective absorption bandwidth is 6.61 GHz.

Conclusions

This study systematically investigated the influence of silicon content on the phase composition, microstructure, and electromagnetic wave absorption properties of SiBCN ceramics, and thoroughly elucidated the underlying absorption mechanisms.

The results demonstrated that after heat treatment at 1600 ℃, the polyborosilazane precursor transformed into a ceramic matrix containing crystalline phases such as Si3N4, SiC, and graphitic carbon. The formation of Si3N4 and SiC crystals significantly increased with increasing silicon content, effectively optimizing the impedance matching characteristics of the ceramics. Concurrently, the graphitization degree of amorphous carbon increased, while the defect density within the ceramic decreased. The formation of numerous nano-sized dielectric grains and heterogeneous interfaces markedly enhanced the electromagnetic wave absorption capacity via strengthening interfacial polarization and conductive loss.

The experimental results indicated that the sample with 38 wt.% silicon content exhibited the optimal comprehensive wave absorption performance: at a thickness of 2.28 mm, the minimum reflection loss (RLmin) reached -54.38 dB at 13.49 GHz. At a thickness of 2.24 mm, the effective absorption bandwidth (EAB) extended to 6.61 GHz. Therefore, the microstructure and phase composition of the ceramics could be effectively regulated via adjusting the silicon content in the precursor, leading to the development of SiBCN ceramic materials with excellent electromagnetic wave absorption properties.

, authors=Yu ZHANG, Ping'an CHEN, Yingli ZHU, Fu CHEN, Mengke QIAO, Jiang WU, Gangtao LUO, Xiangcheng LI, authorsList=Yu ZHANG, Ping'an CHEN, Yingli ZHU, Fu CHEN, Mengke QIAO, Jiang WU, Gangtao LUO, Xiangcheng LI, authorCompany=null, correspAuthors=Ping'an CHEN, Xiangcheng LI, authorNote=

ZHANG Yu (2000-), male, Master candidate. E-mail:

, correspAuthorsNote=
CHEN Ping'an (1986-), male, Ph.D, Professor. E-mail: ;
LI Xiangcheng (1978-), male, Ph.D, Professor.
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SiBCN聚合物衍生陶瓷凭借其在非晶基体中原位生成高介电晶体的特性,形成了独特的“透波-损耗”复合结构,是极具潜力的耐高温电磁波衰减材料。然而,如何精确调控其微观结构以实现最佳吸波性能仍是关键挑战。因此,通过改变聚合物前驱体中Si原子含量,制备不同组分的SiBCN陶瓷,探究Si原子含量对SiBCN陶瓷的物相组成、微观形貌及电磁吸波性能的调控机制。结果表明,高温处理诱导陶瓷内部生成了Si3N4、SiC和石墨碳等晶体。Si元素不仅促进了非晶碳向结晶碳的转化,提高石墨化程度,还有效降低了陶瓷内部的缺陷密度。随着Si含量增加,Si3N4相生成量增多,改善了材料的阻抗匹配特性。优化后SiBCN陶瓷表现出优异的吸波性能:当厚度为2.28 mm时,在13.49 GHz处达到最小反射损耗-54.38 dB;当厚度为2.24 mm时,有效吸收带宽达6.61 GHz。结果表明,通过调控前驱体中Si含量可以优化SiBCN陶瓷的“透波-损耗”结构与阻抗匹配,为该材料在高温吸波领域的实际应用提供了重要的理论依据和实验基础。

, authors=张宇, 陈平安, 朱颖丽, 陈浮, 乔梦珂, 吴江, 罗港涛, 李享成, authorsList=张宇, 陈平安, 朱颖丽, 陈浮, 乔梦珂, 吴江, 罗港涛, 李享成, authorCompany=null, correspAuthors=陈平安, 李享成, authorNote=

张宇(2000—),男,硕士研究生。

, correspAuthorsNote=
陈平安(1986—),男,博士,教授;
李享成(1978—),男,博士,教授。
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硅含量对SiBCN聚合物衍生陶瓷显微结构和电磁性能的影响
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张宇 , 陈平安 , 朱颖丽 , 陈浮 , 乔梦珂 , 吴江 , 罗港涛 , 李享成
硅酸盐学报 | 研究论文 2026,54(9): 3137-3149
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硅酸盐学报 |研究论文 2026 , 54 (9) : 3137 -3149
硅含量对SiBCN聚合物衍生陶瓷显微结构和电磁性能的影响
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张宇 , 陈平安 , 朱颖丽, 陈浮, 乔梦珂, 吴江, 罗港涛, 李享成
作者信息
  • 武汉科技大学,先进耐火材料全国重点实验室,高温电磁材料与结构教育部重点实验室,武汉 430081
通讯作者:
陈平安(1986—),男,博士,教授;
李享成(1978—),男,博士,教授。
作者简介:

张宇(2000—),男,硕士研究生。

Effect of Silicon Content on Microstructure and Electromagnetic Properties of SiBCN Polymer-Derived Ceramics
Yu ZHANG , Ping'an CHEN , Yingli ZHU, Fu CHEN, Mengke QIAO, Jiang WU, Gangtao LUO, Xiangcheng LI
Affiliations
  • The State Key Laboratory of Advanced Refractories, Wuhan University of Science and Technology; Key Laboratory of High Temperature Electromagnetic Materials and Structure of MOE; Wuhan 430081, China
  • Corresponding Author:
    CHEN Ping'an (1986-), male, Ph.D, Professor. E-mail: ;
    LI Xiangcheng (1978-), male, Ph.D, Professor.

    ZHANG Yu (2000-), male, Master candidate. E-mail:

出版时间: 2026-08-18 doi: 10.14062/j.issn.0454-5648.20250803
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SiBCN聚合物衍生陶瓷凭借其在非晶基体中原位生成高介电晶体的特性,形成了独特的“透波-损耗”复合结构,是极具潜力的耐高温电磁波衰减材料。然而,如何精确调控其微观结构以实现最佳吸波性能仍是关键挑战。因此,通过改变聚合物前驱体中Si原子含量,制备不同组分的SiBCN陶瓷,探究Si原子含量对SiBCN陶瓷的物相组成、微观形貌及电磁吸波性能的调控机制。结果表明,高温处理诱导陶瓷内部生成了Si3N4、SiC和石墨碳等晶体。Si元素不仅促进了非晶碳向结晶碳的转化,提高石墨化程度,还有效降低了陶瓷内部的缺陷密度。随着Si含量增加,Si3N4相生成量增多,改善了材料的阻抗匹配特性。优化后SiBCN陶瓷表现出优异的吸波性能:当厚度为2.28 mm时,在13.49 GHz处达到最小反射损耗-54.38 dB;当厚度为2.24 mm时,有效吸收带宽达6.61 GHz。结果表明,通过调控前驱体中Si含量可以优化SiBCN陶瓷的“透波-损耗”结构与阻抗匹配,为该材料在高温吸波领域的实际应用提供了重要的理论依据和实验基础。

硅硼碳氮陶瓷  /  聚合物前驱体  /  硅含量调控  /  电磁波吸收性能
Introduction

SiBCN polymer-derived ceramics (PDCs) are highly promising for high-temperature electromagnetic wave attenuation due to their unique "wave-transmitting/lossy" composite structure, which arises from the in-situ formation of high-dielectric crystals within a low-dielectric amorphous matrix. A critical challenge, however, lies in precisely tailoring their microstructure to maximize absorption performance. To address this issue, SiBCN ceramics were synthesized with different compositions via modulating the silicon (Si) content in the polymer precursors to elucidate the regulatory mechanisms governing phase composition, morphology, and electromagnetic absorption properties. The results reveal that high-temperature treatment induces the crystallization of Si3N4, SiC, and graphitic carbon. The incorporation of Si can facilitate the graphitization of amorphous carbon and effectively reduce internal defect density. Furthermore, an increase in Si content promotes the formation of the Si3N4 phase, thereby enhancing impedance matching. The optimized SiBCN ceramics demonstrate superior microwave absorption capabilities, achieving a minimum reflection loss of -54.38 dB at 13.49 GHz (2.28 mm thickness) and a broad effective absorption bandwidth of 6.61 GHz (2.24 mm thickness). Consequently, this study confirms that tuning the precursor Si content effectively optimizes both the structural configuration and impedance matching of SiBCN ceramics, offering a robust theoretical and experimental foundation for their application in high-temperature environments.

Methods

Under ice bath conditions, 20 g of n-hexane was added to a reaction flask, followed by the sequential addition of dimethyldichlorosilane, boron trichloride, borane dimethyl sulfide complex, and hexamethyldisilazane according to different molar ratios of the raw materials. The mixture was stirred in Ar atmosphere for 24 h. The temperature was then raised to 100 ℃ and maintained for 3 h to remove n-hexane and other by-products. Finally, the temperature increased to 160 ℃ and maintained for 3 h, followed by three cycles of vacuum filtration to obtain a pale yellow resin-like polyborosilazane. A series of polyborosilazanes with different silicon contents were prepared via varying the amount of dimethyldichlorosilane added. The samples with different dimethyldichlorosilane to hexamethyldisilazane molar ratios of 1∶6, 2∶6, and 4∶6 were designated as S30, S38, and S45, with silicon contents of 30%, 38%, and 45%, respectively.

The precursor samples (S30, S38, and S45) were first cured under an N2 atmosphere by heating to 280 ℃ at a rate of 2 ℃/min and holding for 2 h. The cured samples were subsequently heated to 1000 ℃ under an N2 atmosphere at a rate of 5 ℃/min and held for 1 h. They were then further heated to either 1400 or 1600 ℃ at a rate of 2 ℃/min and held for 2 h. The resulting ceramic samples were designated as S30-1400, S38-1400, S45-1400, S30-1600, S38-1600, and S45-1600, respectively.

Results and discussion

The phase composition, microstructure, and electromagnetic properties of the resulting ceramics are regulated via controlling the silicon content in the polymer precursor. The results indicate that after heat treatment in N2 atmosphere at 1600 ℃, crystals such as Si3N4, SiC, and graphitic carbon are formed within the SiBCN ceramics. Silicon promotes the transformation of amorphous carbon into crystalline carbon in the SiBCN ceramics, reduces the defect density within the ceramics, and enhances the graphitization degree. The formation of Si3N4 in the SiBCN ceramics increases with increasing silicon content, improving the impedance matching performance of the ceramics. When the thickness of the SiBCN ceramics is 2.28 mm, the minimum reflection loss reaches -54.38 dB at 13.49 GHz. At a thickness of 2.24 mm, the effective absorption bandwidth is 6.61 GHz.

Conclusions

This study systematically investigated the influence of silicon content on the phase composition, microstructure, and electromagnetic wave absorption properties of SiBCN ceramics, and thoroughly elucidated the underlying absorption mechanisms.

The results demonstrated that after heat treatment at 1600 ℃, the polyborosilazane precursor transformed into a ceramic matrix containing crystalline phases such as Si3N4, SiC, and graphitic carbon. The formation of Si3N4 and SiC crystals significantly increased with increasing silicon content, effectively optimizing the impedance matching characteristics of the ceramics. Concurrently, the graphitization degree of amorphous carbon increased, while the defect density within the ceramic decreased. The formation of numerous nano-sized dielectric grains and heterogeneous interfaces markedly enhanced the electromagnetic wave absorption capacity via strengthening interfacial polarization and conductive loss.

The experimental results indicated that the sample with 38 wt.% silicon content exhibited the optimal comprehensive wave absorption performance: at a thickness of 2.28 mm, the minimum reflection loss (RLmin) reached -54.38 dB at 13.49 GHz. At a thickness of 2.24 mm, the effective absorption bandwidth (EAB) extended to 6.61 GHz. Therefore, the microstructure and phase composition of the ceramics could be effectively regulated via adjusting the silicon content in the precursor, leading to the development of SiBCN ceramic materials with excellent electromagnetic wave absorption properties.

silicon-boron-carbon-nitrogen ceramic  /  polymer precursor  /  silicon content regulation  /  electromagnetic wave absorption performance
张宇, 陈平安, 朱颖丽, 陈浮, 乔梦珂, 吴江, 罗港涛, 李享成. 硅含量对SiBCN聚合物衍生陶瓷显微结构和电磁性能的影响. 硅酸盐学报, 2026 , 54 (9) : 3137 -3149 . DOI: 10.14062/j.issn.0454-5648.20250803
Yu ZHANG, Ping'an CHEN, Yingli ZHU, Fu CHEN, Mengke QIAO, Jiang WU, Gangtao LUO, Xiangcheng LI. Effect of Silicon Content on Microstructure and Electromagnetic Properties of SiBCN Polymer-Derived Ceramics[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (9) : 3137 -3149 . DOI: 10.14062/j.issn.0454-5648.20250803
  • 湖北省重大项目(功能性涂层材料; 2023BAA003)
  • 国家自然科学基金(52304410和51972242)
  • 湖北省青年拔尖人才培养计划
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doi: 10.14062/j.issn.0454-5648.20250803
  • 接收时间:2025-11-02
  • 首发时间:2026-10-22
  • 出版时间:2026-08-18
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  • 收稿日期:2025-11-02
  • 修回日期:2025-11-22
基金
湖北省重大项目(功能性涂层材料; 2023BAA003)
国家自然科学基金(52304410和51972242)
湖北省青年拔尖人才培养计划
作者信息
    武汉科技大学,先进耐火材料全国重点实验室,高温电磁材料与结构教育部重点实验室,武汉 430081

通讯作者:

陈平安(1986—),男,博士,教授;
李享成(1978—),男,博士,教授。
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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
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