Bulk nanocomposites possessing very high hardness in which TiN nanocrystallites are homogeneously embedded in an amorphous Si3N4 matrix are produced from perhydropolysilazane and tetrakisdimethylaminotitanium. That is, a low-molecular-weight TiN molecule is mixed in controlled molar ratio with a polymeric Si3N4 precursor; further processing, including ammonolysis, warm pressing, and controlled nanocrystal growth, yields nanocomposites with the desired properties.

Monolith-type titanium nitride/silicon nitride nanocomposites, denoted as TiN/Si N , 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 °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 Si N 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.