High Temperature Oxidation Behavior And Mechanical Properties Of TiAlN/SiN Decorativefilms On Borosilicate Glass By Magnetron Sputtering

The coated borosilicate glass is an idea substitute of glass-ceramics in the household electrical appliance due to the rich colors and low cost. By controlling deposition parameters, the black TiAlN decorative film can be fabricated on the borosilicate glass in the magnetron sputtering equipment with multiple chambers. The TiAl N film was deposited with a large planar TiAl target with atomic ratio of 1:1 for Ti to Al in the mixing gases of nitrogen and argon. The transparent SiN protective layer also was deposited on the TiAlN film to keep the black color invariant at the high temperature.The films was analysis by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and Nano indentation. The Ti AlN/SiN films include the inner TiAlN layer which has columnar crystals feature with a thickness of 300 nm and the outer amorphous SiN layer with a thickness from 110 nm to 260 nm, but the thickness doesn’t increase linearly with the deposition time. Both TiAlN and SiN layer have dense structure, and the TiAlN is predominant with the orientations of(111),(200),(220) and(222). After the high temperature oxidation, the peak of TiAlN(111) in monolayer film becomes weak, and many pores appear on the surface, oxidation resistance temperature was under 700 °C, both Al2O3 and TiO2 were produced. The coated borosilicate glass with the TiAlN/SiN films still retains the black color after oxidation at 600 °C in atmosphere. While the oxidation temperature elevates to 700 °C, the color of the TiAlN/SiN films begins to change, it is found that large amount of oxide silicon and a little SiO2 were generated on the surface, there is not obvious change of the TiAlN(111) peak. Oxidation Layer is amorphous as the SiN, with the thickness about 5 nm to 10 nm. After the high temperature oxidation at 900 °C, the peak of TiAlN(111) in composite films disappeared, the peak of TiAlN(220) become weak simultaneously. The composite films failure with the disappearance of the columnar crystals feature and the appearance of the Al2O3. After oxidation with a high temperature, the SiO2 and SiOx can be formed on the surface of the SiN layer, and the dense SiO2 structure acts as an effective oxygen diffusion barrier and has a good protection to the inner TiAlN layer. The outer SiN layer plays a role as the barrier against oxygen diffusion into the inner TiAlN layer. The TiAlN film have a hardness of 15.5 GPa, the Ti AlN/SiN films have a hardness of 16 GPa. The oxidation make the monolayer film hardness decreases, but make the composite films hardness increase. The Ti AlN/SiN films have a batter adhesion on the glass substrate than the Ti AlN film.