Molecular-Level Processing of Si-(B)-C Materials with Tailored Nano/Microstructures.

The design of Si-(B)-C materials is investigated, with detailed insight into the precursor chemistry and processing, the precursor-to-ceramic transformation, and the ceramic microstructural evolution at high temperatures. In the early stage of the process, the reaction between allylhydridopolycarbosilane (AHPCS) and borane dimethyl sulfide is achieved. This is investigated in detail through solid-state NMR and FTIR spectroscopy and elemental analyses for Si/B ratios ranging from 200 to 30. Boron-based bridges linking AHPCS monomeric fragments act as crosslinking units, extending the processability range of AHPCS and suppressing the distillation of oligomeric fragments during the low-temperature pyrolysis regime. Polymers with low boron contents display appropriate requirements for facile processing in solution, leading to the design of monoliths with hierarchical porosity, significant pore volume, and high specific surface area after pyrolysis. Polymers with high boron contents are more appropriate for the preparation of dense ceramics through direct solid shaping and pyrolysis. We provide a comprehensive study of the thermal decomposition mechanisms, and a subsequent detailed study of the high-temperature behavior of the ceramics produced at 1000 °C. The nanostructure and microstructure of the final SiC-based ceramics are intimately linked to the boron content of the polymers. B4 C/C/SiC nanocomposites can be obtained from the polymer with the highest boron content.

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.

Transient stages in the chemical vapor deposition of silicon carbide.

Transient CVD experiments were simulated by varying continuously the deposition temperature or the initial gas flow rates (Q(MTS) or Q(H2)). Their consequences on the physicochemical properties of the coatings have been first examined. The adhesion of SiC/SiC bilayers containing these "transient interphases" (phi(Tr)) was investigated by scratch testing. For transient stages resulting from a decrease of Q(MTS) or T, free silicon can be co-deposited in proportions depending on alpha = Q(H2)/Q(MTS), T and P. This phenomenon is related to the high reactivity of the Si bearing species and is activated by high T and P and low a values. In this case, the continuous covalent bonding through the Si-rich interphases preserves the adhesion between the two SiC layers. Transient stages resulting from a decrease of Q(H2) lead first to larger and columnar SiC grains and finally to the deposition of anisotropic carbon, due to the formation of unsaturated hydrocarbons in the gas phase. The interphases with the highest carbon concentrations and thicknesses lead to delamination and local chipping of the outer SiC layer. The poor shear strength of these continuous and anisotropic layers is detrimental to the adherence of the bilayers.