Preceramic polymers, i.e., polymers that are converted into ceramics upon heat treatment, have been successfully used for almost 40 years to give advanced ceramics, especially belonging to the ternary SiCO and SiCN systems or to the quaternary SiBCN system. One of their main advantages is the possibility of combining the shaping and synthesis of ceramics: components can be shaped at the precursor stage by conventional plastic-forming techniques, such as spinning, blowing, injection molding, warm pressing and resin transfer molding, and then converted into ceramics by treatments typically above 800 °C. The extension of the approach to a wider range of ceramic compositions and applications, both structural and thermo-structural (refractory components, thermal barrier coatings) or functional (bioactive ceramics, luminescent materials), mainly relies on modifications of the polymers at the nano-scale, i.e., on the introduction of nano-sized fillers and/or chemical additives, leading to nano-structured ceramic components upon thermal conversion. Fillers and additives may react with the main ceramic residue of the polymer, leading to ceramics of significant engineering interest (such as silicates and SiAlONs), or cause the formation of secondary phases, significantly affecting the functionalities of the polymer-derived matrix.
Full metal-ceramic composite beads containing different amounts of niobium and alumina, particularly 100 vol% alumina, 100 vol% niobium, and 95/5 vol% niobium/alumina, were produced by the alginate gelation process. The suspension for bead fabrication contained sodium alginate as gelling agent and was added dropwise into a calcium chloride solution to trigger the consolidation process. After debinding in air, sintering of the composite beads was performed under inert atmosphere. Samples in green and sintered state were analyzed by digital light microscopy and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. Investigations by mercury intrusion porosimetry revealed that pure alumina beads featured smaller pores compared to composite beads, although the open porosities were comparable. The fracture strength was evaluated on single beads. Contrary to the pure alumina, the composite beads showed a clear plastic deformation. Pure niobium beads showed a ductile behavior with very large deformations. XRD analyses revealed the presence of calcium hexaluminate and beta-alumina as minor phases in the alumina beads, while the composite ones contained about 25 wt% of impurities. The impurities comprised NbO arising from the oxidation, and -Nb2C, from the reaction with the residual sodium alginate.
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