Journal of the American Ceramic Society, Vol.102, No.1, 109-117, 2019
Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti-Si-O ternary glass
Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700 degrees C, then to dark olive green at 800 degrees C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900 degrees C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000 degrees C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900 degrees C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti-K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.