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Research Article | Open Access

Formation of nanocrystalline graphite in polymer-derived SiCN by polymer infiltration and pyrolysis at a low temperature

Mingxing LILaifei CHENG()Fang YE()Conglin ZHANGJie ZHOU
Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern Polytechnical University, Xi’an 710072, China
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Abstract

The microstructure of polymer-derived ceramics (PDCs) was closely related to processing. This study demonstrated that SiCN matrix prepared by polymer infiltration and pyrolysis (PIP) at 900 ℃ inside a Si3N4 whisker (Si3N4w) preform with submicro-sized pores differed from its powder- consolidated analogue in both the content and structure of free carbon. Chemical analysis showed that PIP process had a higher free carbon yield. Raman spectroscopy and transmission electron microscopy (TEM) observation discovered a higher graphitization degree of free carbon and the existence of nanocrystalline graphite in SiCN matrix. Dielectric properties of Si3N4w/SiCN composites were greatly enhanced when volume fraction of SiCN matrix reached 24.5% due to dielectric percolation caused by highly-lossy free carbon. Reconsolidation of hydrocarbon released during pyrolysis by gas-state carbonization in Si3N4 whisker preform was supposed to account for the high yield and graphitization degree of free carbon in PIP process.

References

[1]
Colombo P, Mera G, Riedel R, et al. Polymer-derived ceramics: 40 years of research and innovation in advanced ceramics. J Am Ceram Soc 2010, 93: 1805-1837
[2]
Larson NM, Zok FW. In-situ 3D visualization of composite microstructure during polymer-to-ceramic conversion. Acta Mater 2018, 144: 579-589.
[3]
Kotani M, Inoue T, Kohyama A, et al. Effect of SiC particle dispersion on microstructure and mechanical properties of polymer-derived SiC/SiC composite. Mater Sci Eng: A 2003, 357: 376-385.
[4]
Mera G, Navrotsky A, Sen S, et al. Polymer-derived SiCN and SiOC ceramics—Structure and energetics at the nanoscale. J Mater Chem A 2013, 1: 3826.
[5]
Galusek D, Reschke S, Riedel R, et al. In-situ carbon content adjustment in polysilazane derived amorphous SiCN bulk ceramics. J Eur Ceram Soc 1999, 19: 1911-1921.
[6]
Haluschka C, Kleebe HJ, Franke R, et al. Silicon carbonitride ceramics derived from polysilazanes Part I. Investigation of compositional and structural properties. J Eur Ceram Soc 2000, 20: 1355-1364.
[7]
An L, Riedel R, Konetschny C, et al. Newtonian viscosity of amorphous silicon carbonitride at high temperature. J Am Ceram Soc 1998, 81: 1349-1352.
[8]
Riedel R, Ruswisch LM, An L, et al. Amorphous silicoboron carbonitride ceramic with very high viscosity at temperatures above 1500 ℃. J Am Ceram Soc 1998, 81: 3341-3344.
[9]
Riedel R, Kleebe HJ, Schönfelder H, et al. A covalent micro/nano-composite resistant to high-temperature oxidation. Nature 1995, 374: 526-528.
[10]
Wang Y, Fan Y, Zhang L, et al. Polymer-derived SiAlCN ceramics resist oxidation at 1400 ℃. Scripta Mater 2006, 55: 295-297.
[11]
Haluschka C, Engel C, Riedel R. Silicon carbonitride ceramics derived from polysilazanes Part II. Investigation of electrical properties. J Eur Ceram Soc 2000, 20: 1365-1374.
[12]
Mera G, Riedel R, Poli F, et al. Carbon-rich SiCN ceramics derived from phenyl-containing poly(silylcarbodiimides). J Eur Ceram Soc 2009, 29: 2873-2883.
[13]
Wen Q, Yu Z, Riedel R. The fate and role of in situ formed carbon in polymer-derived ceramics. Prog Mater Sci 2020, 109: 100623.
[14]
Kleebe HJ, Störmer H, Trassl S, et al. Thermal stability of SiCN ceramics studied by spectroscopy and electron microscopy. Appl Organomet Chem 2001, 15: 858-866.
[15]
Gérardin C, Taulelle F, Bahloul D. Pyrolysis chemistry of polysilazane precursors to silicon carbonitride. J Mater Chem 1997, 7: 117-126.
[16]
Cordelair J, Greil P. Electrical conductivity measurements as a microprobe for structure transitions in polysiloxane derived Si-O-C ceramics. J Eur Ceram Soc 2000, 20: 1947-1957.
[17]
Burns GT, Angelotti TP, Hanneman LF, et al. Alkyl- and arylsilsesquiazanes: Effect of the R group on polymer degradation and ceramic char composition. J Mater Sci 1987, 22: 2609-2614.
[18]
Inagaki M, Kang F. Materials Science and Engineering of Carbon: Fundamentals, 2nd edn. Amsterdam (the Netherlands): Elsevier, 2014.
[19]
Li Q, Yin X, Feng L. Dielectric properties of Si3N4-SiCN composite ceramics in X-band. Ceram Int 2012, 38: 6015-6020.
[20]
Li Q, Yin X, Duan W, et al. Improved dielectric properties of PDCs-SiCN by in situ fabricated nano-structured carbons. J Eur Ceram Soc 2017, 37: 1243-1251.
[21]
Liu X, Zhang L, Liu Y, et al. Microstructure and the dielectric properties of SiCN-Si3N4 ceramics fabricated via LPCVD/CVI. Ceram Int 2014, 40: 5097-5102.
[22]
Xue J, Yin X, Pan H, et al. Crystallization mechanism of CVD Si3N4-SiCN composite ceramics annealed in N2 atmosphere and their excellent EMW absorption properties. J Am Ceram Soc 2016, 99: 2672-2679.
[23]
Xue J, Yin X, Ye F, et al. Microstructure and EMW absorption properties of CVI Si3N4-SiCN ceramics with BN interface annealed in N2 atmosphere. J Am Ceram Soc 2018, 101: 1201-1210.
[24]
Xue J, Ren F, Dong Y, et al. Si3N4-BN-SiCN ceramics with unique hetero-interfaces for enhancing microwave absorption properties. Ceram Int 2021, 47: 12261-12268.
[25]
Li M, Cheng L, Ye F, et al. Tailoring dielectric properties of PDCs-SiCN with bimodal pore-structure by annealing combined with oxidation. J Eur Ceram Soc 2020, 40: 5247-5257.
[26]
Duan W, Yin X, Li Q, et al. A review of absorption properties in silicon-based polymer derived ceramics. J Eur Ceram Soc 2016, 36: 3681-3689.
[27]
Hörz M, Zern A, Berger F, et al. Novel polysilazanes as precursors for silicon nitride/silicon carbide composites without “free” carbon. J Eur Ceram Soc 2005, 25: 99-110.
[28]
Konetschny C, Galusek D, Reschke S, et al. Dense silicon carbonitride ceramics by pyrolysis of cross-linked and warm pressed polysilazane powders. J Eur Ceram Soc 1999, 19: 2789-2796.
[29]
Bahloul D, Pereira M, Gerardin C. Pyrolysis chemistry of polysilazane precursors to silicon carbonitride. J Mater Chem 1997, 7: 109-116.
[30]
Delhaes P. Chemical vapor deposition and infiltration processes of carbon materials. Carbon 2002, 40: 641-657.
[31]
Wang T, Li H, Zhang S, et al. The effect of microstructural evolution on micromechanical behavior of pyrolytic carbon after heat treatment. Diam Relat Mater 2020, 103: 107729.
[32]
Zhang P, Zhang L, Yin X. Fabrication of porous Si3N4-Lu2Si2O7 composite ceramics. J Mater Sci Technol 2010, 26: 449-453.
[33]
Zera E, Nickel W, Kaskel S, et al. Out-of-furnace oxidation of SiCN polymer-derived ceramic aerogel pyrolized at intermediate temperature (600-800 ℃). J Eur Ceram Soc 2016, 36: 423-428.
[34]
Moro F, Böhni H. Ink-bottle effect in mercury intrusion porosimetry of cement-based materials. J Colloid Interface Sci 2002, 246: 135-149.
[35]
Needham D, Kinoshita K, Utoft A. Micro-surface and -interfacial tensions measured using the micropipette technique: Applications in ultrasound-microbubbles, oil-recovery, lung-surfactants, nanoprecipitation, and microfluidics. Micromachines 2019, 10: 105.
[36]
Wan J, Gasch MJ, Mukherjee AK. InSitu densification behavior in the pyrolysis consolidation of amorphous Si-N-C bulk ceramics from polymer precursors. J Am Ceram Soc 2004, 84: 2165-2169.
[37]
O’Reilly EP. The electronic structure of amorphous carbon. J Non-Cryst Solids 1987, 97-98: 1095-1102.
[38]
Robertson J. Structural models of a-C and a-C:H. Diam Relat Mater 1995, 4: 297-301.
[39]
Zickler GA, Smarsly B, Gierlinger N, et al. A reconsideration of the relationship between the crystallite size La of carbons determined by X-ray diffraction and Raman spectroscopy. Carbon 2006, 44: 3239-3246.
[40]
Ferrari AC, Robertson J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 2000, 61: 14095-14107.
[41]
Trassl S, Motz G, Rössler E, et al. Characterization of the free-carbon phase in precursor-derived Si-C-N ceramics: I, spectroscopic methods. J Am Ceram Soc 2004, 85: 239-244.
[42]
Gregori G, Kleebe HJ, Brequel H, et al. Microstructure evolution of precursors-derived SiCN ceramics upon thermal treatment between 1000 and 1400 ℃. J Non-Cryst Solids 2005, 351: 1393-1402.
[43]
Gao Y, Mera G, Nguyen H, et al. Processing route dramatically influencing the nanostructure of carbon-rich SiCN and SiBCN polymer-derived ceramics. Part I: Low temperature thermal transformation. J Eur Ceram Soc 2012, 32: 1857-1866.
[44]
Ma B, Zhu Y, Wang K, et al. PIP process greatly influencing the microstructure and electrical conductivity of polymer-derived SiCN ceramics. J Alloys Compd 2019, 784: 1084-1090.
[45]
Hippel ARV. Dielectrics and Waves. London (UK), 1995.
[46]
Kingery WD, Bowen HK, Uhlmann DR, et al. Introduction to ceramics. J Electrochem Soc 1977, 124: 152C.
[47]
Sihvola A. Mixing rules with complex dielectric coefficients. Subsurf Sens Technol Appl 2000, 1: 393-415.
[48]
Bergman DJ. The dielectric constant of a composite material—A problem in classical physics. Phys Rep 1978, 43: 377-407.
[49]
Sihvola A, Saastamoinen S, Heiska K. Mixing rules and percolation. Remote Sens Rev 1994, 9: 39-50.
[50]
Inagaki M, Park KC, Endo M. Carbonization under pressure. New Carbon Mater 2010, 25: 409-420.
[51]
Nomura S, Thomas KM. Some aspects of the generation of coking pressure during coal carbonization. Fuel 1996, 75: 801-808.
[52]
Nomura S, Mahoney M, Fukuda K, et al. The mechanism of coking pressure generation I: Effect of high volatile matter coking coal, semi-anthracite and coke breeze on coking pressure and plastic coal layer permeability. Fuel 2010, 89: 1549-1556.
[53]
Atkins P, De Paula J. Atkins’ Physical Chemistry. Oxford (UK): Oxford University Press, 2010.
[54]
Becker A, Hüttinger KJ. Chemistry and kinetics of chemical vapor deposition of pyrocarbon—V influence of reactor volume/deposition surface area ratio. Carbon 1998, 36: 225-232.
Journal of Advanced Ceramics
Pages 1256-1272
Cite this article:
LI M, CHENG L, YE F, et al. Formation of nanocrystalline graphite in polymer-derived SiCN by polymer infiltration and pyrolysis at a low temperature. Journal of Advanced Ceramics, 2021, 10(6): 1256-1272. https://doi.org/10.1007/s40145-021-0501-2
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