A study of the ceramicisation of allylhydridopolycarbosilane by thermal volatilisation analysis and solid-state nuclear magnetic resonance

Print, Lewis J. and Liggat, John J. and Moug, Stan and Seaton, Helen and Apperley, David C. (2022) A study of the ceramicisation of allylhydridopolycarbosilane by thermal volatilisation analysis and solid-state nuclear magnetic resonance. Silicon, 15 (3). pp. 1355-1379. ISSN 1876-990X (https://doi.org/10.1007/s12633-022-02072-0)

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AHPCS is a pre-ceramic polymer utilised as a precursor to SiC. An initial polymerisation to a cross-linked network is followed by a complex sequence of processes ultimately leading to amorphous SiC. Using thermal volatilisation analysis (TVA) accompanied with solid-state NMR (SSNMR), FTIR, MS, DSC and TGA the complete thermal profile was identified. Between 160 – 300 °C, AHPCS cross-links through the allyl group and undergoes some carbon-silicon rearrangement, with a volatilisation of low mass oligomeric material and significant volumes of hydrogen released from dehydrocoupling of SiH moieties. By 300 °C the allyl group is completely cross-linked but the polymer starts to undergo pyrolytic degradation of the network, with the release of chain fragments and low molar mass species such as methane, ethane, methanol, propane, propene and silane species. Hydrogen once again becomes the major volatile product above 400 °C due to higher proportion of dehydrocoupling forming Si-C and Si-Si bonds. Small chain fragments are seen in the form of larger alkyl silanes. These fragments come from the chain scission of the polymer at weaker parts of the network. The process of side group scission leads to further radical recombination reactions of silicon and carbon atoms to build the SiC network. By 500 °C higher proportion of dehydrocoupling occurs with recombination of Si-Si and Si-C species. The Si-H bonds in -SiH3 groups have completely cleaved along with C-H bonds in the CH3 and CH2 groups leaving SiC, -SiH and HCSi3 present in the material. This bond cleavage leads the silicon and carbon radical species to undergo radical recombination in the network with the volatile release being dominated by H2. By 650 °C the cleavage and recombination of remaining -SiH2-, -SiH- and HCSi¬3 groups ultimately form amorphous SiC. The volatiles released are mostly hydrogen with very few condensable products seen. Finally, SiC is then crystallised at higher temperatures forming β-SiC at 1100 °C and then subsequently α-SiC above 1500 °C.