On the Mass Fractal Character of Si-Based Structural Networks in Amorphous Polymer Derived Ceramics
The intermediate-range packing of SiNxC4−x (0 ≤ x ≤ 4) tetrahedra in polysilycarbodiimide and polysilazane-derived amorphous SiCN ceramics is investigated using 29Si spin-lattice relaxation nuclear magnetic resonance (SLR NMR) spectroscopy. The SiCN network in the polysilylcarbodiimide-derived ceramic consists predominantly of SiN4 tetrahedra that are characterized by a 3-dimensional spatial distribution signifying compact packing of such units to form amorphous Si3N4 clusters. On the other hand, the SiCN network of the polysilazane-derived ceramic is characterized by mixed bonded SiNxC4−x tetrahedra that are inefficiently packed with a mass fractal dimension of Df ~2.5 that is significantly lower than the embedding Euclidean dimension (D = 3). This result unequivocally confirms the hypothesis that the presence of dissimilar atoms, namely, 4-coordinated C and 3-coordinated N, in the nearest neighbor environment of Si along with some exclusion in connectivity between SiCxN4−x tetrahedra with widely different N:C ratios and the absence of bonding between C and N result in steric hindrance to an efficient packing of these structural units. It is noted that similar inefficiencies in packing are observed in polymer-derived amorphous SiOC ceramics as well as in proteins and binary hard sphere systems.
Silicon oxycarbide glasses and glass-ceramics: “All-Rounder” materials for advanced structural and functional applications
Silicon oxycarbides can be considered as being carbon‐containing silicates consisting of glass networks in which oxygen and carbon share bonds with silicon. The carbon‐for‐oxygen substitution in silicate glass networks has been shown to induce significant changes in the network connectivity and consequently strong improvements in the properties of the silicate glass network. For instance, SiOC glasses exhibit Young's moduli, hardness values, glass transition, and crystallization temperatures which are superior to those of vitreous silica. Moreover, the silicon oxycarbide glass network exhibits unique structural features such as reduced mass fractal dimension and nano‐heterogeneity, which significantly affect and/or dictate its properties and behavior. In the present Review, a consideration of the current state of the art concerning the synthesis, processing, and various structural and functional properties of silicon‐oxycarbide‐based glasses and glass‐ceramics is done. Thus, the synthesis of silicon oxycarbides starting from macromolecular precursors such as polysiloxanes or alkoxysilanes‐based sol‐gel systems as well as current advances related to their processing will be critically reviewed. In addition, various structural and functional properties of silicon oxycarbides are presented. Specific emphasis will be put on the intimate correlation between the molecular architecture of the precursors and the structural features and properties of the resulting silicon oxycarbides.
29Si and 17O (Q)CPMG-MAS solid-state NMR experiments as an optimum approach for half-integer nuclei having long T1 relaxation times
Abstract A significantly reduced experiment time for half-integer nuclei with long T 1 relaxation times has been demonstrated by 29 Si CPMG-MAS or 17 O QCPMG-MAS experiments on α-cristobalite, a radiation damaged Zircon and 17 O enriched α-quartz, respectively. For 29 Si up to 37 h were saved compared to the MAS experiment using longer recycle periods (up to 3600 s) but fewer scans. The spectrum reconstructed from the echoes provides similar spectral information as the MAS spectrum. In the 17 O spectrum increased sensitivity facilitated determination of CSA in α-quartz at 9.4 T and points towards a method to obtain natural abundance 17 O spectra of non-cubic oxides.