Phase separation of a hafnium alkoxide-modified polysilazane upon polymer-to-ceramic transformation—A case study

The polymer-to-ceramic transformation of a hafnium alkoxide-modified polysilazane was investigated via thermogravimetric analysis coupled with in situ mass spectrometry (TG/MS), nuclear magnetic resonance (MAS NMR) and transmission electron microscopy (TEM). The results indicate that the structural evolution of the polysilazane upon ceramization is strongly affected by the modification with hafnium alkoxide. Thus, the content of carbon in the ceramic backbone was relatively low, whereas a large amount of SiN4 sites and a segregated carbon phase was present in the sample. Furthermore, this study revealed the formation of a SiHfCNO amorphous single phase ceramic via pyrolysis of the polymer at 700 °C, whereas at higher pyrolysis temperatures precipitation of hafnia was observed, leading to an amorphous hafnia/silicon carbonitride ceramic nanocomposite. The precipitation of hafnia was shown to not rely on decomposition processes, but to be a result of rearrangement reactions occurring within the ceramic material.