Processing and characterization of large diameter ceramic SiCN monofilaments from commercial oligosilazanes

This work reports the processing of large diameter ceramic SiCN monofilaments via the precursor route using two chemically different polysilazanes ML33S and HTTS self-synthesized from respective commercially available oligosilazanes. The melt-spinning of continuous polymer fibers with controllable diameters from 35 to 150 mm and their pyrolysis to ceramic SiCN fibers is not influenced by differences in the chemical structure of the polysilazanes. In contrast, the necessary e-beam curing dose is reduced by Si-vinyl groups from 600 kGy for ML33S (vinyl free) to 200 kGy for HTTS derived polymer fibers. The curing step leads to an enhanced handleability important for further pyrolysis at 1100 degrees C in nitrogen and to an increase in ceramic yield. The resulting ceramic SiCN fibers from both systems have similar mechanical and thermal behavior, indicating quite a low influence of the polysilazane type on these properties. For the first time a comprehensive investigation of the effect of fiber diameter on the tensile strength is reported for SiCN fibers. The average strength increases from similar to 800 MPa for 90 mm diameter fibers to similar to 1600 MPa for the 30 mm diameter fibers. Bend Stress Relaxation (BSR) tests demonstrated that no stress relaxation occurs up to 1000 degrees C for SiCN monofilaments and the creep resistance is equal to or better than commercially available SiC monofilaments produced by chemical vapour deposition (CVD). The oxidation resistance is also comparable to commercially available oxygen free CVD SiC fibers (SCS-6). The ceramic fibers in this study were pyrolyzed at low temperature (1100 degrees C) and have high oxygen content (13 to 29 wt%). The high temperature creep resistance and oxidation resistance is expected to improve if the oxygen content is reduced and the pyrolysis temperature increased.