PYROLYSIS STUDY OF METHYL-SUBSTITUTED SI-H CONTAINING GELS AS PRECURSORS FOR OXYCARBIDE GLASSES, BY COMBINED THERMOGRAVIMETRY, GAS-CHROMATOGRAPHIC AND MASS-SPECTROMETRIC ANALYSIS
R. Campostrini et al., PYROLYSIS STUDY OF METHYL-SUBSTITUTED SI-H CONTAINING GELS AS PRECURSORS FOR OXYCARBIDE GLASSES, BY COMBINED THERMOGRAVIMETRY, GAS-CHROMATOGRAPHIC AND MASS-SPECTROMETRIC ANALYSIS, Journal of materials chemistry, 6(4), 1996, pp. 585-594
Monolithic and transparent gels were prepared by mixing various ethoxi
de silicon precursors containing Si-CH3 and Si-H groups, the compositi
on ensuring the same number of C-H and Si-H bonds. Pyrolysis of these
samples was followed under helium how by connecting thermogravimetry,
gas chromatographic and mass spectrometric analysis, to study the conv
ersion of the gels into oxycarbide materials. In addition to the usual
direct thermal and mass spectra analysis (TG-MS), a TG-GC-MS arrangem
ent, allowing gas chromatographic separation of the species simultaneo
usly evolving during thermodecomposition followed by mass spectral ana
lysis, was successfully achieved. Experimental results indicate that m
ass loss occurs in three steps, each characterized by specific reactio
ns. At low temperatures, densification of the siloxane network derives
from further condensation reactions. At intermediate temperatures, a
remarkable rearrangement of the siloxane chains occurs, with the relea
se of volatile silanes and several siloxane fragments due to Si-H and
Si-O bond exchanges. At higher temperatures, the development of methan
e was detected and attributed to Si-C bond cleavage. Pyrolysis of gels
containing only Si-CH3 or Si-H groups was also studied for comparison
.