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.

Crosslinking chemistry of a liquid poly(vinylmethyl-co-methyl)silazane with an alane hydride-based complex according to Si : Al ratios varying from 5 to 2.5 has been investigated in detail through the characterization of the as-obtained polymers using solid-state NMR, FT-IR and elemental analyses. This reaction allows tailoring the chemical and physical properties of the neat liquid polysilazane while extending its processability to lead to a series of low-temperature formable aluminium-modified polysilazanes. Structural models have been established based on solid-state NMR spectroscopy. Then, pyrolysis under nitrogen occurring the conversion of polymers into ceramics has been studied by coupling TG experiments with FTIR of pyrolysis intermediates. Pyrolysis at 1000 °C leads to X-ray amorphous Al-modified silicon carbonitride materials with higher ceramic yields compared to the materials obtained from the neat polysilazane. However, the increase of the ceramic yield is minimized with the decrease of the Si : Al ratio from 5 to 2.5 in the as-obtained polymers. This is due to the introduction of -NR3 (R = CH3 and C2H5) units as side groups during the polymer synthesis which are released in the low temperature regime of the pyrolysis. The structural evolution of the amorphous network of ceramics has been studied by annealing up to 1800 °C though X-ray diffraction and Raman spectroscopy. Such studies point out that samples remain amorphous even after annealing at 1400 °C (low Si : Al ratio) and 1600 °C (high Si : Al ratio) before forming Si3N4/SiC/AlN and AlN/SiC/C composites after annealing at 1800 °C depending on the Si : Al ratio fixed in the early stage of the process. Dense pieces could be prepared from these low-temperature formable polymers. The latter, especially those containing a certain portion of -NR3 (R = CH3 and C2H5) units acting as plasticizing groups during the process, display appropriate requirements for pressing at low temperature forming dense pieces with hardness and Young's modulus as high as 21.7 GPa and 192.7 GPa, respectively.