Polymer-derived ceramics (PDCs) are a new class of amorphous ceramics in the Si-B-C-N system that are synthesized by the pyrolysis of silicon-based organic polymers. PDCs are lightweight and are resistant to creep, crystallization, and oxidation at temperatures near 1800 K making them ideal for a variety of high temperature applications. In spite of being X-ray amorphous, these materials display structural heterogeneity at the nanometer length scale. Their structure and resulting properties can be drastically altered by the utilization of preceramic polymers with differing chemistry and architectures. Fundamental understanding of the atomic structure is critical in deciphering the structure-property relationships and ultimately in controlling their properties for specific engineering applications. The short-range atomic structure has been extensively investigated using a variety of techniques, however, the structures at length scales beyond next-nearest neighbors remained highly controversial. Here we report the results of a spectroscopic and calorimetric study of short and intermediate -range structure and energetic of SiOC and SiBCN PDCs derived from a wide variety of precursors. SiOC PDCs with different carbon contents were synthesized from polysiloxane precurors and their structures were studied using high-resolution 13C and 29Si nuclear magnetic resonance (NMR) spectroscopy. The results suggest that these PDCs consists of a continuous mass fractal backbone of corner-shared SiC xO4-x tetrahedral units with "voids" occupied by sp 2-hybridized graphitic carbon. The oxygen-rich SiCxO 4-x units are located at the interior of this backbone with a mass fractal dimension of ~ 2.5, while the carbon-rich units occupy the two-dimensional interface between the backbone and the free carbon nanodomains. Such fractal topology is expected to give rise to unusual mechanical and transport properties characteristic of fractal percolation networks. For example, elastic moduli and transport properties such as electrical conductivity and viscosity may show power-law dependence on composition near and above the percolation threshold of the SiOC network or that of the free-carbon phase. Si(B)CN PDCs with different carbon contents were synthesized by pyrolysis of poly(boro)silylcarbodiimides and poly(boro)silazane precursors and their structure and energetics were studied using multi-nuclear, one- and two- dimensional NMR spectroscopy and oxide melt solution calorimetry. The structure of the polysilylcarbodiimide-derived SiCN PDCs at lower carbon content and pyrolysis temperatures (800 oC) consists of amorphous nanodomains of sp2 carbon and silicon nitride with an interfacial bonding between N, C and Si atoms that is stabilized by the presence of hydrogen. The interfacial Si-C and N-C bonds are destroyed with concomitant hydrogen loss upon increasing the pyrolysis temperature to 1100 oC. Calorimetry results demonstrate that the mixed bonding in the interfacial regions play a key role in the thermodynamic stabilization of these PDCs. The size of the carbon domains increases with increasing carbon content until a continuous amorphous carbon matrix is formed with 55-60 wt % C. The polyborosilylcarbodiimide-derived SiBCN ceramics contain carbon and silicon nitride nanodomains with the BN domains being present predominantly at the interface. In contrast, the structure of the polyborosilazane-derived ceramics consists of significant amount of mixed bonding in the nearest-neighbor coordination environments of Si and B atoms leading to the formation of SiC xN4-x tetrahedral units and BCN2 triangular units. The interfacial region between the SiCN and C nanodomains is occupied by the BCN phase. These results demonstrate that the chemistry of the polymeric precursors exerts major influence on the microstructure and bonding in their derived ceramics.
|Advisor:||Navrotsky, Alexandra, Sen, Sabyasachi|
|Commitee:||Castro, Ricardo H.R.|
|School:||University of California, Davis|
|Department:||Materials Science and Engineering|
|School Location:||United States -- California|
|Source:||DAI-B 75/03(E), Dissertation Abstracts International|
|Keywords:||Amorphous, Carbon, Drop solution calorimetry, Nanostructure, Nuclear magnetic resonance, Polymer-derived ceramics|
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