Study of preceramic compositions based on modified polycarbosilane and polyorganosilazanes

Ceramic matrix composites (CMC) exhibit increased crack resistance and resistance to mechanical and thermal shock impacts retaining at the same time the valuable properties of monolithic ceramics. Therefore, they are widely used as parts of heat-loaded elements of aviation and rocket technology, in nuclear power industry, etc. LPI-method (liquid polymer infiltration) of CMC production is based on the impregnation of a skeleton of ceramic fibers with an organosilicon polymer, formation of a preceramic matrix by polymer technology, and subsequent high-temperature pyrolysis resulting in formation of a reinforced ceramic matrix. Ceramics obtained from polymer precursors have a predominantly amorphous structure which determines its high thermal stability. Moreover, introduction of the nanosized particles of carbides, borides and nitrides of refractory metals (Zr, Ti, Hf) into the matrix of a ceramic composite stabilizes its amorphous structure up to temperatures of 1500 - 1600°C. We present the results of studying the preceramic compositions based on polycarbosilane and polyorganosilazanes modified with Hf and Ta atoms. It is shown that introduction of the modifying additives Hf and Ta into the polyorganosilazane composition shifts the curing interval of the compositions towards lower temperatures. The yield of the gel fraction is 73.3 and 82.7 wt.%, respectively. The weight loss of pyrolysate samples heated to 1400°C in air does not exceed 0.5%. The physical and mechanical properties, as well as the thermal oxidative stability of novel ceramic composite materials obtained on the base of the studied compositions and carbon reinforcing filler are analyzed. It is shown that the density of CMC samples increases by 1.5 times with an increase in the number of impregnation cycles and reaches the maximum value of 1950 kg/m³ with five impregnation cycles of the filler with a composition based on polyorganosilazane modified with Ta. The results obtained can be used in the development of new CMCs.

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