Insights into the Microstructural Evolution Occurring during Pyrolysis of Metal-Modified Ceramers Studied through Selective SiO2 Removal

Silicon oxycarbide ceramers containing 5% aluminum, zirconium, and cobalt with respect to the total Si amount are prepared from a commercial polysiloxane and molecular precursors and pyrolyzed at temperatures ranging from 500 to 1000 °C. HF etching is carried out to partially digest the silica phase, thus revealing structural characteristics of the materials, which depend upon the incorporated heteroatom. From the structural and textural characterization, it was deduced that when Al enters into the ceramer structure, the crosslinking degree is increased, leading to lower carbon domain size and carbon incorporation as well. On the contrary, the substitution by Zr induced a phase-separated SiO2-ZrO2 network with some degree of mesoporosity even at high pyrolysis temperatures. Co, however, forms small carbidic crystallites, which strongly modifies the carbonaceous phase in such a way that even when it is added in a small amount and in combination with other heteroatoms, this transient metal dominates the structural characteristics of the ceramer material. This systematic study of the ceramer compounds allows the identification of the ultimate properties of the polymer-derived ceramic composites.