Dense silicon carbonitride ceramics by pyrolysis of cross-linked and warm pressed polysilazane powders

This study reports on the pyrolysis and densifaction behavior of cross-linked poly(hydridomethylsilazane) powders. The influence of the cross-linking procedure such as temperature and annealing time of the polymer powders on the compaction behavior under cold and warm pressing conditions is discussed. The degree of cross-linking is determined by thermal mechanical analysis (TMA). In addition to particle sliding which is assumed to be the compaction mechanism obtained by cold-pressing, the polymer powder consolidates by plastic deformation applying warm-pressing. A continuous 3-dimensional polysilazane network is formed after a dwelling time under these conditions. Pyrolysis of the cross-linked and compacted polysilazane powder in argon at 1100°C gives crack-free amorphous silicon carbonitride Si_3+xC_x+yN₄ with compositions ranging from x=1·47 and y=0·88 for cold pressed samples to x=1·47 and y=1·86 for warm pressed materials. The residual open porosity is significantly reduced from 10–15 vol% in the cold pressed specimens to 1·3–5 vol% by the warm pressing procedure. The weight loss during pyrolysis between room temperature and 1300°C is about 5 wt% lower than that for cold pressed specimens. This result is explained by a reduced methane evolution during the polymer-to-ceramic conversion and is in accordance with the enhanced carbon content of the warm pressed material.