Silicon-Nitrogen Polymers Ceramic Precursors

A less explored area of transition metal catalysis involves bond formation between Group 14 elements and nitrogen. In direct analogy to previously discussed areas of research, silicon-nitrogen bonds can be formed by dehydrocoupling, hydrosilylation, and dehydrogenative silylation. The compounds produced are valuable for use in organic synthesis or as polymer precursors to silicon nitride ceramics. 

X HE USE OF CHEMICAL APPROACHES to improve the processing, properties, and performance of advanced ceramic materials is a rapidly growing area of research and development. One approach involves the preparation of organometallic polymer precursors and their controlled pyrolysis to ceramic materials. This chapter will review the preparation and application of silicon-, carbon-, and nitrogen-containing polymer systems. However, the discussion is not exhaustive the focus is on systems with historical significance or that demonstrate key technological advances. 

There are several structurally different types or polymers that are suitable precursors for ternary Si-C-N ceramics. By far the most investigated precursors are polysilazanes of the general type [Si(R )(R°)N(R°)] (R, R°, R° = H, alkyl, aryl, alkenyl, etc.). In contrast to the limited number of starting compounds, H SiCl(4 ) (x = 0-3) as the silicon source and NH3 or H2N-NH2 as the nitrogen source for synthesis of polysilazanes as precursors for binary Si-N ceramics, the chemistry of polycarbosilazanes, that is, carbon-containing or modified polysilazanes, is very multifaceted. The attachment of various organic groups to the silicon atoms allows adjustment of their physicochemical properties, to control their thermolysis chemistry, and also to influence materials properties. The first... 

Polysilazanes have been shown to be excellent polymeric precursors to amorphous silicon carbonitride (SiCN), silicon nitride, silicon carbide (SiC) and their composites. The actual chemical and phase compositions of the ceramic products depend on the polymer composition and pyrolysis conditions, such as temperature, time and atmosphere. Polymeric silazanes consist of amorphous networks, which transform to amorphous SiCN ceramics by pyrolysis under inert atmosphere at around 1000 C. These ceramic products remain amorphous up to 1400 °C in an inert atmosphere [a.322]. However, at higher temperatures the non-stoichiometric SiCN matrix decomposes, with nitrogen loss, giving the thermodynamically stable phases, namely Si3N4 and SiC. Polysilanes, polycarbosilanes and polysilazanes are commonly used for the preparation of high-performance ceramics such as silicon carbide, silicon nitride and silicon carbonitride. 

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