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.
3D Cf/SiBCN composites prepared by an improved polymer infiltration and pyrolysis
Using liquid poly(methylvinyl)borosilazanes (PMVBSZ) as precursor, carbon fiber reinforced SiBCN matrix composites (Cf/SiBCN) were fabricated by a modified polymer infiltration and pyrolysis (PIP) process. With dicumyl peroxide added as cross-linking agent, the PMVBSZ could be solidified at a low temperature of 120 °C, leading to a high ceramic yield of ~70%. The cross-linking mechanism and ceramization processes of the precursor were investigated in detail. Moreover, a modified infiltration technology was developed, which improved the efficiency and protected the precursor against moist air during PIP. Consequently, the obtained Cf/SiBCN composites had an oxygen content of around 1.22 wt%. Benefiting from the high ceramic yield and high efficiency of the modified PIP, Cf/SiBCN composites with an open porosity of ~10% and uniform microstructure were obtained after only 7 cycles of PIP. The flexural strength and fracture toughness of the derived Cf/SiBCN composites were 371 MPa and 12.9 MPa·m1/2, respectively. This work provides a potential route for the fabrication of high performance Cf/SiBCN composites.
Polytypic transformations in SiC: the role of TEM
Abstract In this paper, the structure of SiC is briefly reviewed and a recent dislocation model for polytypic transformation is explained. The model is based on the asymmetry in the mobility of partial dislocations in SiC. For this reason, the nature of dislocations in SiC is also considered and the asymmetry in dislocation velocity is attributed to the different core structure of the two partial dislocations. Following the description of the polytypic transformation model, some experiments in its support that employ transmission electron microscopy are presented.