COMPOSITION MICROSTRUCTURE PROPERTY RELATIONSHIPS IN CERAMIC MONOFILAMENTS RESULTING FROM THE PYROLYSIS OF A POLYCARBOSILANE PRECURSOR AT 800 TO 1400-DEGREES-C

A 15-mu-m monofilament was extruded from a Yajima's type molten polycarbosilane, stabilized by addition of oxygen and heat-treated at 800 to 1400-degrees-C under an argon atmosphere. Two important phenomena occur during pyrolysis. At 500 to 750-degrees-C, an organic-inorganic state transition takes place with a first weight loss. It yields an amorphous material stable up to about 1100-degrees-C. At this temperature, its composition is close to Si4C5O2. It can be described as a continuum of SiC4 and/or SiC(4-x)O(x) tetrahedral species (and possibly contains free carbon), with a homogeneity domain size less than 1 nm. The amorphous filament exhibits a high strength and semi-conducting properties. Above 1200-degrees-C, a thermal decomposition of the amorphous material takes place with an evolution of gaseous species thought to be mainly SiO and CO, an important cross-section shrinkage and the formation of 7 to 20 nm SiC crystals which are surrounded with a poorly organized turbostratic carbon. The amorphous-crystalline state transition results in a drop in the tensile failure strength and an increase, by four orders of magnitude, in the electrical conductivity which becomes temperature independent. The former effect is due to the crystallization of the filament and the latter to a percolation phenomenon related to the intergranular carbon. The low stiffness is also due to the presence of carbon. It is anticipated that this transition is mainly related to the decomposition of the silicon oxycarbide species. Finally, a 40 to 50 nm layer of turbostratic carbon is formed at the filament surface at 1200 to 1400-degrees-C whose origin remains uncertain. It is thought to be mainly responsible for the formation of the carbon interphase in the high-temperature processing of ceramic matrix composites.