RESUMEN
Boron nitride (BN) ceramic fibers containing amounts of silicon nitride (Si3N4) were prepared using hybrid precursors of poly(tri(methylamino)borazine) (PBN) and polycarbosilane (PCS) via melt-spinning, curing, decarburization under NH3 to 1000 °C and pyrolysis up to 1600 °C under N2. The effect of Si3N4 contents on the microstructure of the BN/Si3N4 composite ceramics was investigated. Series of the BN/Si3N4 composite fibers containing various amounts of Si3N4 from 5 wt% to 25 wt% were fabricated. It was found that the crystallization of Si3N4 could be totally restrained when its content was below 25 wt% in the BN/Si3N4 composite ceramics at 1600 °C, and the amorphous BN/Si3N4 composite ceramic could be obtained with a certain ratio. The mean tensile strength and Young's modulus of the composite fibers correlated positively with the Si3N4 mass content, while an obvious BN (shell)/Si3N4 (core) was formed only when the Si3N4 content reached 25 wt%.
RESUMEN
Continuous ceramic fiber comprising silicon carbide-zirconium carbide (SiC-ZrC) binary phases was obtained through melt spinning, electron-beam curing and pyrolysis of a pre-ceramic precursor of polyzirconocenecarbosilanes (PZCS). After pyrolysis and heat treatment, ZrC particles with mean diameters of 15-20 nm were formed and homogeneously dispersed in a matrix of fine crystalline ß-SiC with an average grain size of 6-10 nm. Concentration of Zr in the fiber varies from 14.88% to 17.45% by mass. Fibers consisting of near-stoichiometric ZrC and SiC with little free carbon can be obtained through pyrolysis decarbonization of the as-cured fiber in hydrogen from room temperature to 1000 °C, and subsequently heat treatment in argon up to 1600 °C for 1 h. High-temperature treatment of these amorphous inorganic fibers leads to crystallization of the binary phases of ß-SiC and ZrC. The removal of free carbon under hydrogen results in more rapid growth of ß-SiC and ZrC crystals, in which obvious aggregation of the dispersed ZrC particles among the continuous ß-SiC matrix can be ascribed to a fast migration of Zr cation.
RESUMEN
Composite ceramic fibers comprising about 80 wt% boron nitride (h-BN) and 20 wt% Si3N4 were fabricated through melt-spinning, electron-beam curing, and pyrolysis up to 1600 °C in atmospheres of NH3 and N2, using a mixture of poly[tri(methylamino)borazine] (PBN) and polysilazane (PSZ). By analyzing the microstructure and composition of the pyrolyzed ceramic fibers, we found the formation of binary phases including crystalline h-BN and amorphous Si3N4. Further investigations confirmed that this heterogeneous microstructure can only be formed when the introduced ratio of Si3N4 is below 30% in mass. The mean modulus and tensile strength of the fabricated composite fibers were about 90 GPa and 1040 MPa, twice the average of the pure h-BN fiber. The dielectric constant and dielectric loss tangent of the composite fibers is 3.06 and 2.94 × 10-3.
RESUMEN
Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.
