Spectroscopic and calorimetric investigation of short and intermediate-range structures and energetics of amorphous SiCO, SiCN, and SiBCN polymer-derived ceramics

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

Filled glass composites for sealing of solid oxide fuel cells.

Glasses filled with ceramic or metallic powders have been developed for use as seals for solid oxide fuel cells (SOFC's) as part of the U.S. Department of Energy's Solid State Energy Conversion Alliance (SECA) Program. The composites of glass (alkaline earth-alumina-borate) and powders ({approx}20 vol% of yttria-stabilized zirconia or silver) were shown to form seals with SOFC materials at or below 900 C. The type and amount of powder were adjusted to optimize thermal expansion to match the SOFC materials and viscosity. Wetting studies indicated good wetting was achieved on the micro-scale and reaction studies indicated that the degree of reaction between the filled glasses and SOFC materials, including spinel-coated 441 stainless steel, at 750 C is acceptable. A test rig was developed for measuring strengths of seals cycled between room temperature and typical SOFC operating temperatures. Our measurements showed that many of the 410 SS to 410 SS seals, made using silver-filled glass composites, were hermetic at 0.2 MPa (2 atm.) of pressure and that seals that leaked could be resealed by briefly heating them to 900 C. Seal strength measurements at elevated temperature (up to 950 C), measured using a second apparatus that we developed, indicated that seals maintained 0.02 MPa (0.2 atm.) overpressures for 30 min at 750 C with no leakage. Finally, the volatility of the borate component of sealing glasses under SOFC operational conditions was studied using weight loss measurements and found by extrapolation to be less than 5% for the projected SOFC lifetime

Effect of demixing and coarsening on the energetics of poly(boro)silazane-derived amorphous Si–(B–)C–N ceramics

Novel poly(boro)silazane-derived Si–(B–)C–N ceramics pyrolyzed at 1100 and 1400 °C were analyzed by multinuclear magic-angle spinning nuclear magnetic resonance spectroscopy and high-temperature oxidative solution calorimetry to investigate the energetic effects of nanodomain structure evolution at two critical pyrolysis temperatures. Like other Si–B–C–N ceramics, increasing pyrolysis temperatures result in the demixing of SiCxN4−x mixed bond environments into SiC4 and SiN4 tetrahedra, interdomain bond cleavage and nanodomain coarsening. Concurrent demixing and domain coarsening, processes detrimental to these ceramics, were found to be energetically stabilizing