Abstract
Monolith-type titanium nitride/silicon nitride nanocomposites, denoted as TiN/Si3N4, have been prepared by a reaction of polysilazanes with a titanium amide precursor, warm pressing of the resultant polytitanosilazanes, and subsequent pyrolysis of the green bodies at 1400 degrees C. Initially, a series of polytitanosilazanes was synthesized and the role of the chemistry behind their synthesis was studied in detail by using solid-state NMR spectroscopy, elemental analysis, and molecular-weight measurements. The intimate relationship between the chemistry and the processability of these precursors is discussed. Polytitanosilazanes display the appropriate requirements for facile processing in solution and as a melt, but they must be treated with liquid ammonia to be adapted for solid-state processing, that is, warm-pressing, to design dense and mechanically stable structures after pyrolysis. We provide a comprehensive mechanistic study of the nanocomposite conversion based on solid-state NMR spectroscopy coupled with thermogravimetric experiments. HRTEM images coupled with XRD and Raman spectroscopy confirmed the unique nanostructural features of the nanocomposites, which appear to be a result of the molecular origin of the materials. The as-obtained samples are composed of an amorphous Si3N4 matrix, in which TiN nanocrystals are homogeneously formed in situ in the matrix during the process. The hardness and Young moduli were measured and are discussed.