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Polyorganoborosilazane ((B[C2H4–Si(CH3)NH]3)n) was synthesized via monomer route from a single-source precursor and thermolyzed at 1300 ℃ in argon atmosphere. The as-thermolyzed Si–B–C–N ceramic was characterized using X-ray diffraction (XRD) and Raman spectroscopy. The crystallization behavior of silicon carbide in the as-thermolyzed amorphous Si–B–C–N matrix was understood by XRD studies, and the crystallite size calculated using Scherrer equation was found to increase from 2 nm to 8 nm with increase in dwelling time. Concomitantly, Raman spectroscopy was used to characterize the free carbon present in the as-thermolyzed ceramic. The peak positions, intensities and full width at half maximum (FWHM) of D and G bands in the Raman spectra were used to study and understand the structural disorder of the free carbon. The G peak shift towards 1600 cm-1 indicated the decrease in cluster size of the free carbon. The cluster diameter of the free carbon calculated using TK (Tuinstra and Koenl) equation was found to decrease from 6.2 nm to 5.4 nm with increase in dwelling time, indicating increase in structural disorder.


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Characterization of free carbon in the as-thermolyzed Si–B–C–N ceramic from a polyorganoborosilazane precursor

Show Author's information Adhimoolam Bakthavachalam KOUSAALYAaRavi KUMARa,*( )Shanmugam PACKIRISAMYb
Materials Processing Section, Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, Tamil Nadu, India
Analytical Spectroscopy and Ceramics Group, PCM Entity, Vikram Sarabhai Space Centre, Thiruvananthapuram 695022, India

Abstract

Polyorganoborosilazane ((B[C2H4–Si(CH3)NH]3)n) was synthesized via monomer route from a single-source precursor and thermolyzed at 1300 ℃ in argon atmosphere. The as-thermolyzed Si–B–C–N ceramic was characterized using X-ray diffraction (XRD) and Raman spectroscopy. The crystallization behavior of silicon carbide in the as-thermolyzed amorphous Si–B–C–N matrix was understood by XRD studies, and the crystallite size calculated using Scherrer equation was found to increase from 2 nm to 8 nm with increase in dwelling time. Concomitantly, Raman spectroscopy was used to characterize the free carbon present in the as-thermolyzed ceramic. The peak positions, intensities and full width at half maximum (FWHM) of D and G bands in the Raman spectra were used to study and understand the structural disorder of the free carbon. The G peak shift towards 1600 cm-1 indicated the decrease in cluster size of the free carbon. The cluster diameter of the free carbon calculated using TK (Tuinstra and Koenl) equation was found to decrease from 6.2 nm to 5.4 nm with increase in dwelling time, indicating increase in structural disorder.

Keywords:

synthesis, polyorganoborosilazane, precursor-derived ceramic, Si–B–C–N, Raman spectroscopy, free carbon
Received: 15 May 2013 Revised: 11 August 2013 Accepted: 20 August 2013 Published: 04 December 2013 Issue date: December 2013
References(47)
[1]
Houtz RC. “Orlon” acrylic fiber: Chemistry and properties. Text Res J 1950, 20: 786-801.
[2]
Ezekiel HM, Spain RG. Preparation of graphite fibers from polymeric fibers. J Polym Sci Pol Sym 1967, 19: 249-265.
[3]
Verbeek W. Production of shaped articles of homogeneous mixtures of silicon carbide and nitride. U.S. Patent 3853567 A, Nov. 1973.
[4]
Verbeek W, Winter G. Formkoerper aus siliciumcarbid und verfahren zu ihrer herstellung. DE Patent 2236078 A1, July 1974.
[5]
Yajima S, Hayashi J, Imori M. Continuous silicon carbide fiber of high tensile strength. Chem Lett 1975, 4: 931-934.
[6]
Hayashi J, Omori M, Yajima S. Siliciumcarbidfasern und verfahren zur herstellung derselben. DE Patent 2618150 A1, April 1976.
[7]
Yajima S, Hayashi J, Omori M, et al. Development of a silicon carbide fiber with high tensile strength. Nature 1976, 261: 683-685.
[8]
Bernard S, Weinmann M, Cornu D, et al. Preparation of high-temperature stable Si–B–C–N fibers from tailored single source polyborosilazanes. J Eur Ceram Soc 2005, 25: 251-256.
[9]
Bernard S, Weinmann M, Gerstel P, et al. 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: 289-299.
[10]
Miele P, Bernard S, Cornu D, et al. Recent developments in polymer-derived ceramic fibers (PDCfs): Preparation, properties and applications— A review. Soft Mater 2007, 4: 249-286.
[11]
Sarkar S, Zhai L. Polymer-derived non-oxide ceramic fibers—Past, present and future. Mater Express 2011, 1: 18-29.
[12]
Mucalo MR, Milestone NB, Vickridge IC, et al. Preparation of ceramic coatings from pre-ceramic precursors. J Mater Sci 1994, 29: 4487-4499.
[13]
Hauser R, Borchard SN, Riedel R, et al. Polymer-derived SiBCN ceramic and their potential application for high temperature membranes. J Ceram Soc Jpn 2006, 114: 524-528.
[14]
Torrey JD, Bordia RK. Processing of polymer-derived ceramic composite coatings on steel. J Am Ceram Soc 2008, 91: 41-45.
[15]
Schütz A, Günthner M, Motz G, et al. Characterisation of novel precursor-derived ceramic coatings with glass filler particles on steel substrates. Surf Coat Technol 2012, 207: 319-327.
[16]
Riedel R, Kienzle A, Dressler W, et al. A silicoboron carbonitride ceramic stable to 2,000 ℃. Nature 1996, 382: 796-798.
[17]
Müller A, Gerstel P, Weinmann M, et al. Correlation of boron content and high temperature stability in Si–B–C–N ceramics. J Eur Ceram Soc 2000, 20: 2655-2659.
[18]
Müller A, Gerstel P, Weinmann M, et al. Correlation of boron content and high temperature stability in Si–B–C–N ceramics II. J Eur Ceram Soc 2001, 21: 2171-2177.
[19]
Wang Z-C, Aldinger F, Riedel R. Novel silicon–boron–carbon–nitrogen materials thermally stable up to 2200 ℃. J Am Ceram Soc 2001, 84: 2179-2183.
[20]
Cai Y, Zimmermann A, Prinz S, et al. Nucleation phenomena of nano-crystallites in as-pyrolysed Si–B–C–N ceramics. Scripta Mater 2001, 45: 1301-1306.
[21]
Butchereit E, Nickel KG, Müller A. Precursor-derived Si–B–C–N ceramics: Oxidation kinetics. J Am Ceram Soc 2001, 84: 2184-2188.
[22]
Ramakrishnan PA, Wang YT, Balzar D, et al. Silicoboron–carbonitride ceramics: A class of high-temperature, dopable electronic materials. Appl Phys Lett 2001, 78: 3076.
[23]
Ravi Kumar NV, Mager R, Cai Y, et al. High temperature deformation behavior of crystallized Si–B–C–N ceramics obtained from a boron modified poly(vinyl)silazane polymeric precursor. Scripta Mater 2004, 51: 65-69.
[24]
Saha A, Raj R, Williamson DL. A model for the nanodomains in polymer-derived SiCO. J Am Ceram Soc 2006, 89: 2188-2195.
[25]
Kumar R, Mager R, Phillipp F, et al. High-temperature deformation behavior of nanocrystalline precursor-derived Si–B–C–N ceramics in controlled atmosphere. Int J Mater Res 2006, 97: 626-631.
[26]
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.
[27]
Hermann AM, Wang Y-T, Ramakrishnan PA, et al. Structure and electronic transport properties of Si–(B)–C–N ceramics. J Am Ceram Soc 2001, 84: 2260-2264.
[28]
Wang Y, Wang K, Zhang L, et al. Structure and optical property of polymer-derived amorphous silicon oxycarbides obtained at different temperatures. J Am Ceram Soc 2011, 94: 3359-3363.
[29]
Peng J. Thermochemistry and constitution of precursor-derived Si–(B–)C–N ceramics. Ph.D. Thesis. Stuttgart (Germany): Universität Stuttgart, 2002.
[30]
Trassl S, Motz G, Rössler E, et al. Characterization of the free-carbon phase in precursor-derived SiCN ceramics: I, spectroscopic methods. J Am Ceram Soc 2002, 85: 239-244.
[31]
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.
[32]
Sarkar S, Gan Z, An L, et al. Structural evolution of polymer-derived amorphous SiBCN ceramics at high temperature. J Phys Chem C 2011, 115: 24993-25000.
[33]
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.
[34]
Kumar R, Cai Y, Gerstel P, et al. Processing, crystallization and characterization of polymer derived nano-crystalline Si–B–C–N ceramics. J Mater Sci 2006, 41: 7088-7095.
[35]
Tunistra F, Koenig JL. Raman spectrum of graphite. J Chem Phys 1970, 53: 1126-1130.
[36]
Pócsik I, Hundhausen M, Koós M, et al. Origin of the D peak in the Raman spectrum of microcrystalline graphite. J Non-Cryst Solids 1998, 227–230: 1083-1086.
[37]
Ferrari AC. Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun 2007, 143: 47-57.
[38]
Jiang T, Wang Y, Wang Y, et al. Quantitative Raman analysis of free carbon in polymer-derived ceramics. J Am Ceram Soc 2009, 92: 2455-2458.
[39]
Robertson J. Hard amorphous (diamond-like) carbons. Prog Solid State Ch 1991, 21: 199-333.
[40]
Ferrari AC, Robertson J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 2000, 61: 14095-14107.
[41]
Ferrari AC, Robertson J. Raman spectroscopy of amorphous, nanostructured, diamond-like carbon, and nanodiamond. Phil Trans R Soc Lond A 2004, 362: 2477-2512.
[42]
Matthews MJ, Pimenta MA, Dresselhaus G, et al. Origin of dispersive effects of the Raman D band in carbon materials. Phys Rev B 1999, 59: R6585-R6588.
[43]
Ma Y, Wang S, Chen Z. Raman spectroscopy studies of the high-temperature evolution of the free carbon phase in polycarbosilane derived SiC ceramics. Ceram Int 2010, 36: 2455-2459.
[44]
Pimenta MA, Dresselhaus G, Dresselhaus MS, et al. Studying disorder in graphite-based systems by Raman spectroscopy. Phys Chem Chem Phys 2007, 9: 1276-1290.
[45]
Trassl S, Motz G, Rössler E, et al. Characterisation of the free-carbon phase in precursor-derived SiCN ceramics. J Non-Cryst Solids 2001, 293–295: 261-267.
[46]
Casiraghi C, Pisana S, Novoselov KS, et al. Raman fingerprint of charged impurities in grapheme. Appl Phys Lett 2007, 91: 233108.
[47]
Ravi Kumar NV, Prinz S, Cai Y, et al. Crystallization and creep behavior of Si–B–C–N ceramics. Acta Mater 2005, 53: 4567-4578.
Publication history
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Publication history

Received: 15 May 2013
Revised: 11 August 2013
Accepted: 20 August 2013
Published: 04 December 2013
Issue date: December 2013

Copyright

© The author(s) 2013

Acknowledgements

We gratefully acknowledge the financial support from the Vikram Sarabhai Space Centre, Thiruvananthapuram through ISRO-IITM cell (Project No. ICSR/ISRO-IITM/MET/08-09/122/RAVK). We also would like to acknowledge the Department of Physics, IIT-M for performing Raman spectroscopy.

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