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Improved thermal stability of SiBCN ceramics by lowering nitrogen content

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Abstract

Polymer-derived SiBCN ceramics are well known for their outstanding thermal stability. Although they possess outstanding thermal stability, SiBCN ceramics are easily to decompose out Si3N4 and SiC crystalline phases at high temperature leading to thermal stability worsen. Here, to reduce the Si3N4 crystallization precipitation in SiBCN ceramics, the N contents are reduced from 25 to 8.09 wt%, 11.44 and 14.51 wt%, by adding polycarbosilane into polyborosilazane, respectively. The experimental results illustrated that the precipitation temperature of Si3N4 phase in modified S1–S3 ceramics increased to 1800 °C which was higher than that of S0 ceramics (1600 °C). The results indicated that the crystalline precipitation of Si3N4 in SiBCN ceramics can be suppressed at a high-temperature environment via declining N content, which may provide a new strategy for decreasing carbothermal reduction. In addition, the original SiBCN ceramic had a weight change of 31.7% at T > 1800 °C, while the weight change of modified SiBCN ceramics significantly reduced to 15.7 ~ 19.5%, which attributed to the decrease in carbothermal reduction.

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References

  1. Riedel R, Kienzle A, Dressler W et al (1996) A silicoboron carbonitride ceramic stable to 2,000ºC. Nature 382:796–798

    Article  CAS  Google Scholar 

  2. Colombo P, Gabriela M, Riedel R et al (2010) Polymer-derived ceramics: 40 years of research and innovation in advanced ceramics. J Am Ceram Soc 69:1805–1837

    Google Scholar 

  3. Baldus HP, Wagner O, Jansen M (1992) Synthesis of advanced ceramics in the systems Si-B-N and Si-B-N-C employing novel precursor compounds. Mrs Online Proceedings Library Arch, 271

  4. Christ M, Thurn F, Weinmann M et al (2000) High-temperature mechanical properties of Si-B-C-N precursor-derived amorphous ceramics and the applicability of deformation models developed for metallic glasses. J Am Ceram Soc 83:266–297

    Article  Google Scholar 

  5. Li DX, Jia DC, Yang ZH et al (2021) Principles, design, structure and properties of ceramics for microwave absorption or transmission at high-temperatures. Int Mater 67:2184–2188

    Google Scholar 

  6. Schmidt H, Borchardt G, Kaistasow O et al (2007) Atomic of Boron and other constituents in amorphous Si-B-C-N. J Non Cryst Solids 353:4801–4805

    Article  CAS  Google Scholar 

  7. Schmidt H, Borchardt G, Baurmann H et al (2001) Tracer self-diffusion studies in amorphous Si-(B)-C-N ceranics using ion implantaion and SIMS. Def Diff Forum 941:194–199

    Google Scholar 

  8. Viard A, Fonblanc D, Schmidt M et al (2018) Polymer derived Si-B-C-N ceramics:30 years of research. Adv Eng Mater 20:1800360

    Article  Google Scholar 

  9. Weinmann M, Schuhmacher J, Kummer H et al (2000) Synthesis of thermal behavior of novel Si-B-C-N ceramic precursors. Chem Mater 12:623–632

    Article  CAS  Google Scholar 

  10. Zhao H, Chen LX, Luan MXG et al (2017) Synthesis, pyrolysis of a novel liquid SiBCN ceramic precursor and its application in ceramic matrix composites. J Eur Ceram Soc 37:1321–1329.

  11. Tan X, Liu W, Cao LM et al (2018) Oxidation behavior of a 2D-SiCf/BN/SiBCN composite at 1350–1650ºC in air. Mater Corros 69:1227–1236

    Article  CAS  Google Scholar 

  12. Ding Q, Ni DW, Dong SM et al (2018) Mechanical properties and microstructure evolution of 3D Cf/SiBCN composites at elevated temperatures. J Am Ceram Soc 101:4699–4707

    Article  CAS  Google Scholar 

  13. Jia Y, Ji XY, Gou YZ et al (2019) High-temperature properties and interface evolution of C/SiBCN composites prepared by precursor infiltration and pyrolysis. J Eur Ceram Soc 39:4645–4653

    Article  CAS  Google Scholar 

  14. Jia Y, Ji XY, Chen SA et al (2019) Preparation of C/SiBCN composites by precursor infiltration and pyrolysis using a novel precursor. MaterRes Express 6:065612–065612

    Article  CAS  Google Scholar 

  15. Lee SH, Weinmann M, Aldinger F (2008) Processing and properties of C/Si–B–C–N fiber–reinforced ceramic matrix composites prepared by precursor impregnation and pyrolysis. Acta Mater 56:1529–1538

    Article  CAS  Google Scholar 

  16. Aldinger F, Weinmann M, Horz M (2002) Dehydrocoupling of tris(hydridosilylethyl)boranes and cyanamide: a novel access to boron-containing polysilylcarbodiimides. J Organomet Chem 659:29–42

    Article  Google Scholar 

  17. Kumar R, Aldinger F, Phillipp F (2007) Oxidation induced effects on the creep properties of nano-crystalline porous Si–B–C–N ceramics. MSEA 445:251–258

    Article  Google Scholar 

  18. Ding Q, Ni DW, Dong SM et al (2018) Effect of interphase on mechanical properties and microstructures of 3D Cf/SiBCN composites at elevated temperatures. J Am Ceram Soc 102:3630–3640

    Article  Google Scholar 

  19. Muller A, Gerstel P, Weinmann M et al (2000) Correlation of boron content and higher temperature stability in Si-B-C-N ceramics. J Eur Ceram Soc 20:2655–2659

    Article  CAS  Google Scholar 

  20. Puerta AR, Remsen EE, Bradley MG et al (2003) Synthesis and ceramic conversion reactions of 9-BBN-modified allylhydridopolycarbosilane: a new single-source precursor toboron-modified silicon carbide. Chem Mater 15:478–485.

  21. Gerstel P, Muller A, Bill J et al (2003) Synthesis and high-temperature behavior of Si/B/C/N precursor-derived ceramics without “Free Carbon”. Chem Mater 15:4980–4986

    Article  CAS  Google Scholar 

  22. Daxin Li, Zhihua Yang, Dechang Jia et al (2018) Carbon content-dependent microstructures, surface characteristics and thermal stability of mechanical alloying derived SiBCN powders. Ceram Int 44:3614–3624.

  23. Petrman V, Houska J, Kos S et al (2011) Effect of nitrogen content on electronic structure and properties of SiBCN materials. Acta Mater 59:2341–2349

    Article  CAS  Google Scholar 

  24. Liu YP, Shuai Y, Cui C et al (2018) Influence of silicon sources on structures and properties of polyborosilazane precursor derived SiBNC ceramic fiber. Ceram Int 44:21381–21385

    Article  Google Scholar 

  25. Cao SY (2012) Synthesis and ceramization of liquid hyperbranched polycarbosilanes [M]. National University of Defense Technology

  26. Li HL, Zhang L, Cheng Y et al (2007) Effect of the polycarbosilane structure on its final ceramic yield. J Eur Ceram Soc 28:887–891

    Article  Google Scholar 

  27. Choong NS, Corriu RJ, Leclercq D et al (2002) Silicon carbonitride from polymeric precursors: thermal cross-linking and pyrolysis of oligosilazane model compounds. Chem Mater 4:141–146

    Article  Google Scholar 

  28. Zhao H, Chen LX, Luan XG et al (2017) Synthesis, pyrolysis of a novel liquid SiBCN ceramic precursor and its application in ceramic matrix composites. J Eur Ceram Soc 37:1321–1329

    Article  CAS  Google Scholar 

  29. He WL, Chen T, Peng F (2018) Borazine-type single source precursor with vinyl to SiBCN ceramic. J Ceram Soc Jpn 126:253–259.

    Article  CAS  Google Scholar 

  30. Zhou CH, Min L, Yang M et al (2014) Dimethylaminoborane-modified copolysilazane as a novel precursor for high-temperature resistant SiBCN ceramics. J Eur Ceram Soc 34:3579–3589

    Article  CAS  Google Scholar 

  31. Wan JM, Gasch J, Mukherjee AK (2002) Effect of ammonia treatment on the crystallization of amorphous silicon–carbon–nitrogen ceramics derived from polymer precursor pyrolysis. J Am Ceram Soc 85:554–564

    Article  CAS  Google Scholar 

  32. Antoine VF, Diane S, Marion L et al (2017) Molecular chemistry and engineering of boron-modified Polyorganosilazanes as new processable and functional SiBCN precursors. Chem Eur J 23:9076–9090

    Article  Google Scholar 

  33. Gervais CF, Babonneau L, Ruwisch R et al (2003) Solid-state NMR investigations of the polymer route to SiBCN ceramics. Can J Chem 81:1359–1369

    Article  CAS  Google Scholar 

  34. Kumar RY, Cai P, Gerstel G et al (2006) Processing, crystallization and characterization of polymer derived nano-crystalline Si-B-C-N ceramics. J Mater Sci 41:7088–7095

    Article  CAS  Google Scholar 

  35. Sen S, Widgeon S (2015) On the mass fractal character of Si-based structural networks in amorphous polymer derived ceramics. Nanomaterials 5:366–375

    Article  CAS  Google Scholar 

  36. Zhong XX, Pei Y, Miao L et al (2017) Accelerating the crosslinking process of hyperbranched polycarbosilane by UV irradiation. J Eur Ceram Soc 37:3263–3270

    Article  CAS  Google Scholar 

  37. Kleebe HJ, Turquat C, Sorar GD (1991) Phase separation in a SiCO glass studied by transmission electron microscopy and electron energy-loss spectroscopy. J Am Ceram Soc 74:670–673

    Google Scholar 

  38. Wang BJ, Song YJ, Zhang X et al (2022) Polymer derived SiBCN(O) ceramics with tunable element content. Ceram Int 48:10280–10287

    Article  CAS  Google Scholar 

  39. Ma Y, Wang S, Chen ZH (2011) In situ growth of a carbon interphase between carbon fibers and a polycarbosilane-derived silicon carbide matrix. Carbon 49:2869–2872.

    Article  Google Scholar 

Download references

Acknowledgements

The authors sincerely thank navi-sci.cn for its contributions to assistance with the test.

Funding

This work is supported by the National Natural Science Foundation of China (Grant No. 52173306), the National Key Research and Development Program of China (Grant No. 2021YFB3702304-4) and the National Science and Technology Major Project (Grant No. J2019-VI-0017–0132).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Xiangtan University, Xiangtan, 411105, People’s Republic of China

    Tingbo Wang & Weiguo Mao

  2. Science and Technology on Advanced Ceramic Fibers & Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha, 410073, People’s Republic of China

    Tingbo Wang, Si’an Chen, Zikai Zhao & Qingsong Ma

  3. College of Materials Science and Engineering, Changsha University of Science & Technology, Changsha, 410114, People’s Republic of China

    Weiguo Mao

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  1. Tingbo Wang
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  2. Si’an Chen
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Correspondence to Si’an Chen.

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Prime Novelty Statement:The carbothermal reduction in SiBCN ceramics at high temperatures severely limits their use in aerospace applications. This paper presents a simple and effective method to improve thermal stability by reducing the elemental N content of derived SiBCN ceramics. Meanwhile, the microstructural evolution and high-temperature behavior of SiBCN ceramics with different elements contents is investigated systematically. The experimental result demonstrates that the carbothermal reduction (mainly via 2C + 2Si–N → 2SiC + N2) can be hindered via decreasing the elemental N contents in the SiBCN ceramics. This is because the dehydrocoupling degree between Si–H and N–H is significant reduced in pyrolysis process, thus decreasing precipitation of Si–N at high-temperature environment, which may provide a new strategy for decreasing carbothermal reduction.

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Wang, T., Chen, S., Zhao, Z. et al. Improved thermal stability of SiBCN ceramics by lowering nitrogen content. J Mater Sci 58, 1013–1025 (2023). https://doi.org/10.1007/s10853-022-08027-5

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