Synthesis, Elemental Doping of Polyborosilazane and Applications of the Resulting SiBCN Ceramics

ZENG Guan-jie; ZHAO Yang-zhong; ZHANG Jian-ning; SONG Yu-jie

doi:10.14028/j.cnki.1003-3726.2025.25.049

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Synthesis, Elemental Doping of Polyborosilazane and Applications of the Resulting SiBCN Ceramics

更新时间：2025-06-25

- Synthesis, Elemental Doping of Polyborosilazane and Applications of the Resulting SiBCN Ceramics
- Polymer Bulletin Vol. 38, Issue 7, Pages: 1073-1092(2025)
- 作者机构：
  
  1.宁波杭州湾新材料研究院，宁波 315336
  2.中国科学院宁波材料技术与工程研究所，宁波 315201
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.049
  CLC：
- Received：14 February 2025，
  
  Accepted：25 March 2025，
  
  Published Online：30 May 2025，
  
  Published：20 July 2025
- 稿件说明：
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曾冠杰, 赵泱中, 张健宁, 宋育杰. 聚硼硅氮烷的合成、元素掺杂及其衍生SiBCN陶瓷的应用. 高分子通报, 2025, 38(7), 1073–1092.

Zeng, G, J.; Zhao, Y. Z.; Zhang, J. N.; Song, Y. J. Synthesis, elemental doping of polyborosilazane and applications of the resulting SiBCN ceramics. Polym. Bull. (in Chinese), 2025, 38(7), 1073–1092.
曾冠杰, 赵泱中, 张健宁, 宋育杰. 聚硼硅氮烷的合成、元素掺杂及其衍生SiBCN陶瓷的应用. 高分子通报, 2025, 38(7), 1073–1092. DOI： 10.14028/j.cnki.1003-3726.2025.25.049.

Zeng, G, J.; Zhao, Y. Z.; Zhang, J. N.; Song, Y. J. Synthesis, elemental doping of polyborosilazane and applications of the resulting SiBCN ceramics. Polym. Bull. (in Chinese), 2025, 38(7), 1073–1092. DOI： 10.14028/j.cnki.1003-3726.2025.25.049.

摘要

聚合物前驱体转化法推动了SiBCN陶瓷在高温结构材料、功能涂层、热管理材料和高温传感器等领域的应用发展。通过前驱体聚硼硅氮烷分子结构的设计改性可以实现对SiBCN陶瓷微观组分和结构的调控。本文综述了SiBCN陶瓷前驱体聚硼硅氮烷的合成方法、异质元素掺杂路线以及前驱体转化SiBCN陶瓷的成型和应用，探讨了前驱体分子结构、异质元素与SiBCN陶瓷微观结构之间的关系。最后，总结了聚硼硅氮烷及其衍生SiBCN陶瓷在现阶段研究中存在的问题，并结合未来需求展望了发展方向。

Abstract

The polymer precursor conversion method has propelled the development of SiBCN ceramics in various fields including high-temperature structural materials

functional coatings

thermal management materials

and high-temperature sensors. The design of the molecular structure of the precursor polysilazane enables the regulation of the microstructure and composition of SiBCN ceramics. This review summarizes the synthesis methods of SiBCN ceramic precursors (polysilazanes)

doping routes of heteroatoms

and processing and applications of SiBCN ceramics. It also explores the relationship between the molecular structure of the precursor

heteroatoms

and the microstructure of the resulting SiBCN ceramics. Finally

the current challenges in the research on polysilazanes and their derived SiBCN ceramics are summarized

and potential future directions are discussed in light of future demands.

关键词

Keywords

references

Ratzker, B. ; Sokol, M . Exploring the capabilities of high-pressure spark plasma sintering (HPSPS): a review of materials processing and properties . Mater. Design. , 2023 , 233 , 112238 .

Han, J. C. ; Liu, C. ; Bradford-Vialva, R. L. ; Klosterman, D. A. ; Cao, L . Additive manufacturing of advanced ceramics using preceramic polymers . Materials , 2023 , 16 ( 13 ), 4636 .

Liu, Y. ; Lin, X. ; Gong, H. ; Zhang, Y. ; Feng, Y. ; Mao, J. ; Xie, B . Electromagnetic properties and microwave absorption performances of nickel-doped SiCN ceramics pyrolyzed at different temperatures . J. Alloy. Compd. , 2019 , 771 , 356 – 363 .

Hu, J. ; Liu, C. ; Ye, F. ; Cheng, L. ; Wei, Y . A review on high-performance SiCf/SiC composites prepared by PIP process . J. Mater. Res. Technol. , 2024 , 33 , 7216 – 7235 .

Wójcik-Bania, M . Influence of the addition of organo-montmorillonite nanofiller on cross-linking of polysiloxanes-FTIR studies . Spectrochim. Acta. A , 2021 , 252 , 119491 .

Zhou, Y. ; Lu, K . Polymer-derived high-temperature nonoxide materials: a review . Adv. Eng. Mater. , 2023 , 25 ( 9 ), 2200967 .

Colombo, P. ; Mera, G. ; Riedel, R. ; Sorarù, G. D . Polymer-derived ceramics: 40 years of research and innovation in advanced ceramics . J. Am. Ceram. Soc. , 2010 , 93 ( 7 ), 1805 – 1837 .

Xiao, S. ; Dai, Z. ; Li, D. ; Zhang, F. ; Yang, L. ; Ren, X . Electrical and optical property of lanthanum oxide doped potassium sodium niobate ceramics . J. Inorg. Mater. , 2022 , 37 ( 5 ), 520 .

Ma, J. ; Zhang, B. P. ; Chen, J. Y . Excess Bi and cooling method on phase structure and electrical properties of BiFeO 3 -BaTiO 3 lead-free ceramics . J. Inorg. Mater. , 2017 , 32 ( 10 ), 1035 .

Guo, X. ; Bao, W. ; Liu, J. ; Wang, X. ; Zhang, G. ; Xu, F . Study on the solid solution structures of high-entropy ceramics by transmission electron microscopy . J. Inorg. Mater. , 2021 , 36 ( 4 ), 365 .

Viard, A. ; Fonblanc, D. ; Lopez-Ferber, D. ; Schmidt, M. ; Lale, A. ; Durif, C. ; Balestrat, M. ; Rossignol, F. ; Weinmann, M. ; Riedel, R. ; Bernard, S . Polymer derived Si―B―C―N ceramics: 30 years of research . Adv. Eng. Mater. , 2018 , 20 ( 10 ), 1800360 .

Dou, W. ; Li, D. ; Wang, B. ; Yang, Z. ; Chen, J. ; Jia, D. ; Riedel, R. ; Zhou, Y . Novel Csf/SiBCN composites prepared by densifying Csf/MA-SiBCN with the PIP process: Oxidation behavior and damage mechanism . J. Adv. Ceram. , 2024 , 13 ( 5 ), 666 – 678 .

Zhao, Z. ; Ma, Q. ; Wang, T. ; Long, X. ; Shao, C. ; Chen, S . Microstructure and properties of SiBCN/SiBCN mini-composites prepared by the precursor infiltration and the pyrolysis process . J. Am. Ceram. Soc. , 2024 , 107 ( 4 ), 2052 – 2057 .

Niu, Z. ; Li, D. ; Jia, D. ; Yang, Z. ; Lin, K. ; Wang, Y. ; Colombo, P. ; Riedel, R. ; Zhou, Y . Three-dimensional PDC-SiBCN network in MA-SiBCN ceramics: Toughening-reinforcing effect and oxidation barrier . J. Eur. Ceram. Soc. , 2025 , 45 ( 4 ), 117053 .

Li, Y. ; Yan, L. ; Song, M. ; Chen, S. ; Guo, A. ; Hou, F. ; Ye, L. ; Han, W. ; Liu, J . Integration of thermal protection and structural health monitoring for carbon fiber reinforced SiBCN composites with SiC coating enhanced interfacial performance . Ceram. Int. , 2023 , 49 ( 13 ), 21678 – 21687 .

Riedel, R. ; Kienzle, A. ; Dressler, W. ; Ruwisch, L. ; Bill, J. ; Aldinger, F . A silicoboron carbonitride ceramic stable to 2, 000 ℃ . Nature , 1996 , 382 ( 6594 ), 796 – 798 .

Tavakoli, A. H. ; Gerstel, P. ; Golczewski, J. A. ; Bill, J . Kinetic effect of boron on the thermal stability of Si―(B―) C―N polymer-derived ceramics . Acta. Mater. , 2010 , 58 ( 18 ), 6002 – 6011 .

Haug, J. ; Lamparter, P. ; Weinmann, M. ; Aldinger, F . Diffraction study on the atomic structure and phase separation of amorphous ceramics in the Si―(B)―C―N system. 2. Si―B―C―N ceramics . Chem. Mater. , 2004 , 16 ( 1 ), 83 – 92 .

Haug, J. ; Lamparter, P. ; Weinmann, M. ; Aldinger, F . Diffraction study on the atomic structure and phase separation of amorphous ceramics in the Si―(B)―C―N system. 1. Si―C―N ceramics . Chem. Mater. , 2004 , 16 ( 1 ), 72 – 82 .

Su, K. ; Remsen, E. E. ; Zank, G. A. ; Sneddon, L. G . Synthesis, characterization, and ceramic conversion reactions of borazine-modified hydridopolysilazanes: new polymeric precursors SiNCB ceramic composites . Chem. Mater. , 1993 , 5 ( 4 ), 547 – 556 .

Legrow, G. E. ; Lim, T. F. ; Lipowitz, J. ; Reaoch, R. S . Ceramics from hydridopolysilazane . Am. Ceram. Soc. Bull. , 1987 , 66 ( 2 ), 363 – 367 .

Srivastava, D. ; Duesler, E. N. ; Paine, R. T . Synthesis of silylborazines and their utilization as precursors to silicon-containing boron nitride . Eur. J. Inorg. Chem. , 1998 , ( 6 ), 855 – 859 .

Haberecht, J. ; Nesper, R. ; Grützmacher, H . A construction kit for Si―B―C―N ceramic materials based on borazine precursors . Chem. Mater. , 2005 , 17 ( 9 ), 2340 – 2347 .

He, W. ; Chen, L. ; Xu, T. ; Peng, F . Borazine-type single source precursor with vinyl to SiBCN ceramic . J. Ceram. Soc. Jpn. , 2018 , 126 ( 4 ), 253 – 259 .

Yu, Z. ; Ma, M. ; Liu, Z. ; Zhang, Z. ; Luo, C. ; Zhang, T. ; Kong, J . Hyperbranched polyborosilazanes derived SiBCN ceramic for high-temperature wave-transparent performance . J. Mater. Sci. Technol. , 2024 , 196 , 162 – 170 .

Wang, Y. ; Luo, C. ; Wu, Y. ; Hu, X. ; Wang, L. ; Chen, X. ; Chao, M. ; Liu, G. ; Hu, Y. ; Yan, L . High temperature stable, amorphous SiBCN microwave absorption ceramics with tunable carbon structures derived from divinylbenzene crosslinked hyperbranched polyborosilazane . Carbon , 2023 , 213 , 118189 .

Baldus, H. P. ; Wagner, O. ; Jansen, M . Synthesis of advanced ceramics in the systems Si―B―N and Si―B―N―C employing novel precursor compounds . MRS Online Proceedings Library (OPL) , 1992 , 271 , 821 – 826 .

Baldus, P. ; Jansen, M. ; Sporn, D . Ceramic fibers for matrix composites in high-temperature engine applications . Science , 1999 , 285 ( 5428 ), 699 – 703 .

Baldus, H. P. ; Jansen, M. ; Wagner, O . New materials in the system Si―(N, C)―B and their characterization . Key Eng. Mater. , 1993 , 89 , 75 – 80 .

Müller, U. ; Weinmann, M. ; Jansen, M . Cl2MeSi-NH-BCl2 and ClMe2Si-NH-BCl2: novel processable single source precursors of amorphous Si/C/B/N ceramics . J. Mater. Chem. , 2008 , 18 ( 31 ), 3671 .

Weinmann, M. ; Schuhmacher, J. ; Kummer, H. ; Prinz, S. ; Peng, J. Q. ; Seifert, H. J. ; Christ, M. ; Müller, K. ; Bill, J. ; Aldinger, F . Synthesis and thermal behavior of novel Si―B―C―N ceramic precursors . Chem. Mater. , 2000 , 12 ( 3 ), 623 – 632 .

Bernard, S. ; Weinmann, M. ; Gerstel, P. ; Miele, P. ; Aldinger, F . Boron-modified polysilazane as a novel single-source precursor for SiBCN ceramic fibers: synthesis, melt-spinning, curing and ceramic conversion . J. Mater. Chem. , 2005 , 15 ( 2 ), 289 – 299 .

Bernard, S. ; Weinmann, M. ; Cornu, D. ; Miele, P. ; Aldinger, F . Preparation of high-temperature stable SiBCN fibers from tailored single source polyborosilazanes . J. Eur. Ceram. Soc. , 2005 , 25 ( 2-3 ), 251 – 256 .

Gottardo, L. ; Bernard, S. ; Gervais, C. ; Inzenhofer, K. ; Motz, G. ; Weinmann, M. ; Balan, C. ; Miele, P . Chemistry, structure and processability of boron-modified polysilazanes as tailored precursors of ceramic fibers . J. Mater. Chem. , 2012 , 22 ( 16 ), 7739 – 7750 .

Gottardo, L. ; Bernard, S. ; Gervais, C. ; Weinmann, M. ; Miele, P . Study of the intermediate pyrolysis steps and mechanism identification of polymer-derived SiBCN ceramics . J. Mater. Chem. , 2012 , 22 ( 34 ), 17923 – 17933 .

Ouyang, T. ; Gottardo, L. ; Bernard, S. ; Chiriac, R. ; Balan, C. ; Miele, P . Evaluation of the processability of boron-containing organosilazane polymers based on shear rheology . J. Appl. Polym. Sci. , 2013 , 128 ( 1 ), 248 – 257 .

Viard, A. ; Gottardo, L. ; Lopez-Ferber, D. ; Soleilhavoup, A. ; Salameh, C. ; Samal, S. ; Gueguen, Y. ; Rouxel, T. ; Motz, G. ; Babonneau, F. ; Gervais, C. ; Bernard, S . Molecular design of melt-spinnable co-polymers as Si―B―C―N fiber precursors . Dalton. T. , 2017 , 46 ( 39 ), 13510 – 13523 .

Majoulet, O. ; Sandra, F. ; Bechelany, M. C. ; Bonnefont, G. ; Fantozzi, G. ; Joly-Pottuz, L. ; Malchère, A. ; Bernard, S. ; Miele, P . Silicon-boron-carbon- nitrogen monoliths with high, interconnected and hierarchical porosity . J. Mater. Chem. A. , 2013 , 1 ( 36 ), 10991 – 11000 .

Dang, Y. ; Li, T. ; Zhao, Y. ; Duan, L. ; Zhang, J. ; Chen, K. ; He, L. ; Huang, Q. ; Zhao, C. ; Song, Y . Polyborosilazanes with controllable B/N ratio for Si-B-C-N ceramics . Materials , 2023 , 16 ( 3 ), 1053 .

Duan, L. ; Li, T. ; Zhao, Y. ; Dang, Y. ; Zhang, J. ; Chen, K. ; Xu, J. ; Huang, Q. ; Zhao, C. ; Song, Y . Polyborosilazane with broadly tunable boron content for SiBCN ceramics . Inorg. Chem. , 2023 , 62 ( 25 ), 10014 – 10020 .

Zhao, Y. ; Li, T. ; Dang, Y. ; Wu, E. ; Sun, J. ; Zhang, X. ; Du, S. ; Liu, X. ; Yi, X. ; Cui, P. ; Song, Y. ; He, L . UV-curable polyborosilazane precursors for SiBCN coatings under harsh environments . ACS Appl. Polym. Mater. , 2023 , 5 ( 3 ), 2166 – 2176 .

Kong, J. ; Wang, M. ; Zou, J. ; An, L . Soluble and meltable hyperbranched polyborosilazanes toward high-temperature stable SiBCN ceramics . ACS Appl. Mater. Interfaces. , 2015 , 7 ( 12 ), 6733 – 6744 .

Xu, J. ; Yu, Y. ; Huang, L. ; Zhang, S . Dielectric and electromagnetic properties of amorphous PDCs-Si(Al)CNO with different Al contents in X-band . Ceram. Int. , 2022 , 48 ( 18 ), 25872 – 25879 .

Ding, J. ; Chen, F. ; Chen, J. ; Liang, J. ; Kong, J . MXene-derived TiC/SiBCN ceramics with excellent electro-magnetic absorption and high-temperature resistance . J. Am. Ceram. Soc. , 2021 , 104 ( 4 ), 1772 – 1784 .

Miao, Y. ; Yang, Z. ; Zhu, Q. ; Liang, B. ; Li, Q. ; Tian, Z. ; Jia, D. ; Cheng, Y. ; Zhou, Y . Thermal ablation behavior of SiBCN-Zr composites prepared by reactive spark plasma sintering . Ceram. Int. , 2017 , 43 ( 11 ), 7978 – 7983 .

Houska, J. ; Mares, P. ; Simova, V. ; Zuzjakova, S. ; Cerstvy, R. ; Vlcek, J . Dependence of characteristics of MSiBCN (M=Ti, Zr, Hf) on the choice of metal element: Experimental and ab-initio study . Thin Solid Films , 2016 , 616 , 359 – 365 .

Tang, Z. ; Wang, S. ; Tusiime, R. ; Hu, J. ; Chen, H. ; Zhang, Y. ; Zhang, H. ; Liu, Y . Synthesis of SiBNC-Al ceramics with different aluminum contents via polymer-derived method . J. Am. Ceram. Soc. , 2022 , 105 ( 4 ), 2914 – 2924 .

Lyu, Y. ; Cheng, Y. ; Zhao, G. ; Wang, M. ; Chen, G. ; Zhang, X. ; Han, W . Modification of SiBCN by Zr atom and its effect on ablative resistance of Cf/SiBCN(Zr) composites . Compos. Part B-Eng. , 2023 , 253 , 110511 .

Song, Y. ; Liu, Z. ; Zhang, X. ; Zhu, R. ; Zhang, Y. ; Liu, P. ; He, L. ; Kong, J . Single source precursor derived SiBCNHf ceramic with enhanced high-temperature microwave absorption and antioxidation . J. Mater. Sci. Technol. , 2022 , 126 , 215 – 227 .

Liu, Y. ; Tang, Z. ; Wang, S. ; Tusiime, R. ; Shen, J. ; Hu, J. ; Chen, H. ; Zhang, Y. ; Han, K . Synthesis and characterization of a novel preceramic polymer for SiBNC-Ti ceramics . J. Inorg. Organomet. P. , 2022 , 32 ( 2 ), 646 – 655 .

Lu, Y. ; Wang, X. ; Zhang, X. ; Lu, X. ; Han, W. ; Hao, J. ; Zhao, T . Tribological behavior of Cu-modified polymer-derived SiBCN ceramics at elevated temperature . Tribol. Int. , 2023 , 185 , 108540 .

Liu, C. ; Tong, Y. ; Liu, C. ; Xu, M. ; Sun, H. ; Wu, S. ; Zhao, Y; Li, J. ; Guo, X. ; Feng, Y . Heterogeneous interface engineering of SiBCN/Ni fibers extends enhanced electromagnetic wave absorption properties . Colloid. Surface. A. , 2024 , 695 , 134234 .

Shi, H. ; Chen, S. ; Yan, Q. ; Meng, S. ; Lin, S. ; Li, J . Evolution of dielectric properties of SiBCN ceramics and its derived wireless passive temperature sensor application . Ceram. Int. , 2024 , 50 ( 23 ), 51516 – 51524 .

Yan, Q. ; Chen, S. ; Shi, H. ; Wang, X. ; Meng, S. ; Li, J . Fabrication of polymer-derived SiBCN ceramic temperature sensor with excellent sensing performance . J. Eur. Ceram. Soc. , 2023 , 43 ( 16 ), 7373 – 7380 .

Jiang, J. ; Yan, L. ; Li, J. ; Xue, Y. ; Zhang, C. ; Hu, X. ; Guo, A. ; Du, H. ; Liu, J . Lightweight, thermally insulating SiBCN/Al 2 O 3 ceramic aerogel with enhanced high-temperature resistance and electromagnetic wave absorption performance . Chem. Eng. J. , 2024 , 501 , 157656 .

Liu, H. ; Zhang, Y. ; Liu, X. ; Duan, W. ; Li, M. ; Zhou, Q. ; Li, S. ; Wang, G. ; Han, G . Additive manufacturing of nanocellulose/polyborosilazane derived CNFs-SiBCN ceramic metamaterials for ultra-broadband electromagnetic absorption . Chem. Eng. J. , 2022 , 433 , 133743 .

Hanniet, Q. ; Petit, E. ; Calas-Etienne, S. ; Etienne, P. ; Aissou, K. ; Gervais, C. ; Miele, P. ; Charlot, B. ; Salameh, C . Rational design of SiBCN microstructures using direct photolithography of patternable preceramic photoresists . Mater. Design. , 2022 , 223 , 111234 .

Song, Y. ; Zhu, R. ; Liu, Z. ; Dai, X. ; Kong, J . Phase-transformation nanoparticles synchronously boosting mechanical and electromagnetic performance of SiBCN ceramics . ACS Appl. Mater. Interfaces. , 2023 , 15 ( 3 ), 4234 – 4245 .

Luan, X. ; Zhao, Q. ; Gu, S. ; Dong, X. ; Cheng, L. ; Riedel, R . Microstructure-electrical conductivity relationship of Si(Ni)BCN ceramics . Ceram. Int. , 2024 , 50 ( 7 ), 10055 – 10066 .

Dang, Y. ; Li, T. ; Yu, C. ; Zhao, Y. ; Ruan, H. ; Song, Y . Facile synthesis of dense SiBCN coatings with excellent compactness, smoothness, and high-temperature inertness on defective graphite surfaces . Surf. Interfaces. , 2024 , 50 , 104473 .

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