Resumen
High-Si-content transition metal nitride coatings, which exhibited an X-ray amorphous phase, were proposed as protective coatings on glass molding dies. In a previous study, the Zr–Si–N coatings with Si contents of 24–30 at.% exhibited the hardness of Si3N4, which was higher than those of the middle-Si-content (19 at.%) coatings. In this study, the bonding characteristics of the constituent elements of Zr–Si–N coatings were evaluated through X-ray photoelectron spectroscopy. Results indicated that the Zr 3d5/2 levels were 179.14–180.22 and 180.75–181.61 eV for the Zr–N bonds in ZrN and Zr3N4 compounds, respectively. Moreover, the percentage of Zr–N bond in the Zr3N4 compound increased with increasing Si content in the Zr–Si–N coatings. The Zr–N bond of Zr3N4 dominated when the Si content was >24 at.%. Therefore, high Si content can stabilize the Zr–N compound in the M3N4 bonding structure. Furthermore, the thermal stability and chemical inertness of Zr–Si–N coatings were evaluated by conducting thermal cycle annealing at 270 °C and 600 °C in a 15-ppm O2–N2 atmosphere. The results indicated that a Zr22Si29N49/Ti/WC assembly was suitable as a protective coating against SiO2–B2O3–BaO-based glass for 450 thermal cycles.