The preparation of HfC/C ceramics via molecular design

Polymer derived ceramics have received lots of attention throughout the last few decades. Unfortunately, only a few precursor systems have been developed, focusing on silicon based polymers and ceramics, respectively. Herein, the synthesis of novel hafnium containing organometallic polymers by two different approaches is reported. Dialkenyl substituted hafnocene monomers were synthesized and subsequently polymerized via a free radical mechanism. Salt metathesis reactions of hafnocene dichloride with bifunctional linkers led to the formation of polymeric materials. NMR spectroscopic methods - in solution as well as in the solid state - were used to characterize the organometallic polymers. Ceramics were finally obtained after cross-linking and thermal treatment under argon (T = 1800 °C). SEM investigations, elemental analyses, Raman spectroscopy and XRD investigations identified the pyrolyzed products as partially crystalline HfC/C mixed phases. © 2011 The Royal Society of Chemistry.