Superparamagnetic Silicon Carbonitride Ceramic Fibers Through In Situ Generation of Iron Silicide Nanoparticles During Pyrolysis of an Iron-Modified Polysilazane.

Ceramic fibers are high-tech structural key components of ceramic matrix composites (CMCs), which are a very promising class of materials for applications in next-generation turbines, especially nonoxide ceramic fibers, usually produced by the polymer-derived ceramics (PDC) route, which possess the enhanced mechanical and thermostructural properties necessary to withstand the harsh conditions (temperature and atmosphere) imposed on CMCs. However, recycling composite materials, such as fiber-reinforced polymers and CMCs, is still a big challenge. Here, we present for the first time the processing of superparamagnetic iron-containing ceramic fibers, which, due to their magnetic properties, can be separated from the matrix material of a composite. The synthesis strategy of the novel functional ceramic fibers is based on a tailored reaction of polyorganosilazane with an iron complex, resulting in a suitable, meltable polymer. After melt-spinning and curing, subsequent pyrolysis leads to superparamagnetic ceramic fibers with a saturation magnetization of 1.54 emu g-1 because of in situ-formed iron silicide nanoparticles of an average size of 7.5 nm, homogeneously dispersed in an amorphous SiCNO matrix. Moreover, the ceramic fibers exhibit a tensile strength of 1.24 GPa and appropriate oxidation resistance. The developed versatile reaction strategy allows also for the incorporation of other elements to implement further functionalities for processing of multifunctional composites.

Molecular design of melt-spinnable co-polymers as Si-B-C-N fiber precursors.

Two series of co-polymers with the general formula [B(C2H4SiCH3(NH)x(NCH3)y)3]n, i.e., composed of C2H4SiCH3(NH)x and C2H4SiCH3(NCH3)y (C2H4 = CHCH3, CH2CH2) building blocks in a well defined x : y ratio, have been synthesized by hydroboration of dichloromethylvinylsilane with borane dimethyl sulfide followed by successive reactions with lithium amide and methylamine according to controlled ratios. The role of the chemistry behind their syntheses has been studied in detail by solid-state NMR, FT-IR and elemental analyses. Then, the intimate relationship between the chemistry and the melt-spinnability of these polymers was discussed. By keeping x = 0.50 and increasing y above 0.50, i.e., obtaining methylamine excess, the co-polymers contained more ending groups and especially more tetracoordinated boron, thus allowing tuning very precisely the chemical structure of the preceramic polymer in order to meet the requirements for melt-spinning. The curing treatment under ammonia at 200 °C efficiently rendered the green fibers infusible before their subsequent pyrolysis under nitrogen at 1000 °C to generate Si-B-C-N ceramic fibers. Interestingly, it could be possible to produce also low diameter hollow fibers with relatively high mechanical properties for a further exploration as membrane materials.

Molecular Chemistry and Engineering of Boron-Modified Polyorganosilazanes as New Processable and Functional SiBCN Precursors.

A series of boron-modified polyorganosilazanes was synthesized from a poly(vinylmethyl-co-methyl)silazane and controlled amounts of borane dimethyl sulfide. The role of the chemistry behind their synthesis has been studied in detail by using solid-state NMR spectroscopy, FTIR spectroscopy, and elemental analysis. The intimate relationship between the chemistry and the processability of these polymers is discussed. Polymers with low boron contents displayed appropriate requirements for facile processing in solution, such as impregnation of host carbon materials, which resulted in the design of mesoporous monoliths with a high specific surface area after pyrolysis. Polymers with high boron content are more appropriate for solid-state processing to design mechanically robust monolith-type macroporous and dense structures after pyrolysis. Boron acts as a crosslinking element, which offers the possibility to extend the processability of polyorganosilazanes and suppress the distillation of oligomeric fragments in the low-temperature region of their thermal decomposition (i.e., pyrolysis) at 1000 °C under nitrogen. Polymers with controlled and high ceramic yields were generated. We provide a comprehensive mechanistic study of the two-step thermal decomposition based on a combination of thermogravimetric experiments coupled with elemental analysis, solid-state NMR spectroscopy, and FTIR spectroscopy. Selected characterization tools allowed the investigation of specific properties of the monolith-type SiBCN materials.