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.
A Model for the Nanodomains in Polymer‐Derived SiCO
The polymer-based synthesis of ceramics such as SiCO (and SiCN) leads to the incorporation of significant amounts of carbon into their molecular structure. A key feature of the nanostructure of these polymer-derived ceramics is the revelation of persistent, 1-5 nm size domains by small-angle X-ray scattering. Here we present a model for these nanodomains, which is consistent with the nuclear magnetic resonance (NMR) data and with the phenomenological properties of SiCO (high resistance to creep and viscoelastic behavior). The model consists of clusters of silica tetrahedra encased within an interdomain wall constituted from mixed bonds of SiCO, and from a network of sp 2 carbon. The model predicts the domain size as a function of the carbon content. These predictions are in reasonable agreement with the measurements of the nanodomains in SiCO synthesized with varying carbon contents (the domain size decreases with higher carbon). Simple maps are developed for easy reading of the domain size and the width of the interdomain boundary in the composition diagrams.
Composite monolayer fabrication by an arc-spray process
A single layer (monotape) technique for fabricating complex high-temperature tungsten-fiber-reinforced superalloy composites is proposed. The fabrication of sheets of arc-sprayed monotape 38 cm wide and 122 cm long has been demonstrated. Composites fabricated using the method are shown to have equal tensile strength and a cleaner matrix than composites fabricated from powder metal cloth monotapes, and the present technique is less expensive than the powder metal fabrication techniques.