The pyrolytic conversion of vinyl-terminated poly[hydridomethylsiloxane-co-vinylmethylsiloxane] (PSO) into SiOC ceramic at various heating rates has been investigated by thermogravimetry coupled with mass spectrometry. Kinetic analysis on pyrolysis process of PSO has been conducted by peak-fitting method. The results show that all the experimental derivative thermogravimetric curves recorded at five different heating rates can be best fitted by four Gaussian functions. The activation energy for each peak was determined by an isoconversional method, and kinetic models for Peaks 1 and 2 were investigated on the basis of Master plots. The results show that Peak 1 was governed by R2-type mechanisms, while Peak 2 followed diffusion-type transport mechanisms. Plausible chemical pathways for the evolved gases within these peaks are also discussed. The release of a large amount of carbon-containing species was identified in the temperature ranges corresponding to Peak 2 and 4, which are associated with the mineralization and ceramization steps, respectively. The transition from mineralization to ceramization process occurs in the region of Peak 3, and is accompanied by the evolution of H2.
Polysiloxane Pyrolytic process Kinetic analysis Peak fitting
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The authors acknowledge the final supports from the National Science Foundation of China (50973114, 50973113), the Ministry of Science and Technology of China (2010CB934705, 2012CB933200) and the Chinese Academy of Sciences.
Hasegawa Y, Imura M, Yajima S. Synthesis of continuous silicon-carbide fibre. 2. Conversion of polycarbosilane fibre into silicon-carbide fibres. J Mater Sci. 1980;5:720–8.CrossRefGoogle Scholar
Wang K, Günthner M. High performance environmental barrier coating. Part II. Active filler loaded SiOC system for superalloys. J Eur Ceram Soc. 2011;31:3003–10.CrossRefGoogle Scholar
Wu J, Li Y, Chen L, Zhang Z, Wang D, Xu C. Simple fabrication of micro/nano-porous SiOC foam from polysiloxane. J Mater Chem. 2012;22:6542–5.CrossRefGoogle Scholar
Su D, Li YL. Pyrolytic transformation of liquid precursors to shaped bulk ceramics. J Eur Ceram Soc. 2010;30:1503–11.CrossRefGoogle Scholar
Riedel R, Passing G, Schoenfelder H, Brook RJ. Synthesis of dense silicon-based ceramics at low temperatures. Nature. 1992;355:714–6.CrossRefGoogle Scholar
Li XD, Edirisinghe MJ. Structural evaluation of polysilane-derived products: from amorphous to thermodynamically stable phases. Philos Mag. 2004;84:647–71.CrossRefGoogle Scholar
Perejon A, Sanchez-Jimenez PE, Criado JM, Perez-Maqueda LA. Kinetic analysis of complex solid-state reactions: a new deconvolution procedure. J Phys Chem B. 2011;115:1780–91.CrossRefGoogle Scholar
Bernard S, Fiaty K, Cornu D, Miele P. Kinetic modeling of the polymer-derived ceramics route: investigation of the thermal decomposition kinetics of poly[B-(methylamino)borazine] precursors into boron nitride. J Phys Chem B. 2006;110:9048–60.CrossRefGoogle Scholar
Soraru GD, Pederiva L. Pyrolysis kinetics for the conversion of a polymer into an amorphous silicon oxycarbide ceramic. J Am Ceram Soc. 2002;85:2181–7.CrossRefGoogle Scholar
Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.CrossRefGoogle Scholar
Chen FX, Zhou CR, Li GP. Study on thermal decomposition and the non-isothermal decomposition kinetics of glyphosate. J Therm Anal Calorim. 2012;109:1457–62.CrossRefGoogle Scholar
Doyle CD. Series approximations to the equation of thermogravimetric data. Nature. 1965;207:290–1.CrossRefGoogle Scholar
Gotor FJ, Criado JM, Málek J, Koga N. Kinetic analysis of solid-state reactions: the universality of master plots for analyzing isothermal and nonisothermal experiments. J Phys Chem A. 2000;104:10777–82.CrossRefGoogle Scholar
Málek J, Mitsuhashi T, Criado JM. Kinetic analysis of solid-state processes. J Mater Res. 2001;16:1862–71.CrossRefGoogle Scholar
Senum GI, Yang RT. Rational approximations of the integral of the Arrhenius function. J Thermal Anal. 1977;11:445–7.CrossRefGoogle Scholar
Hu Y, Li W, Hu J. Resolving overlapped spectra with curve fitting. Spectrochim Acta A. 2005;62:16–21.CrossRefGoogle Scholar
Plawsky JL, Wang F, Gill WN. Kinetic model for the pyrolysis of polysiloxane polymers to ceramic composites. AIChE J. 2002;48:2315–23.CrossRefGoogle Scholar
Bahloul-Hourlier D, Latournerie J, Dempsey P. Reaction pathways during the thermal conversion of polysiloxane precursors into oxycarbide ceramics. J Eur Ceram Soc. 2005;25:979–85.CrossRefGoogle Scholar