Cr–Si–N coatings were prepared through reactive direct current magneton sputtering using a high N₂/Ar flow ratio of 1. The addition of Si to improve the mechanical properties and oxidation resistance of Cr–N coatings was examined. The results indicated that the Cr–Si–N coatings with an Si content of 50 at % exhibited a cubic CrN phase with a columnar structure, whereas the coatings with 14 at % Si comprised of a nanocomposite structure, and the coatings with 16–18 at % Si were near-amorphous. The nanocomposite Cr₃₂Si₁₄N₅₄ coating possessed hardness and Young’s modulus values of 17 and 209 GPa, respectively, accompanied with a hardness to effective Young’s modulus (H/E*) value of 0.077 and an elastic recovery (We) level of 55%—all the properties were highest within the as-deposited coating. The addition of Si was also beneficial to reduce the surface roughness and improve the oxidation resistance.

ZrN_x (x = 0.67–1.38) films were fabricated through direct current magnetron sputtering by a varying nitrogen flow ratio [N₂/(Ar + N₂)] ranging from 0.4 to 1.0. The structural variation, bonding characteristics, and mechanical properties of the ZrN_x films were investigated. The results indicated that the structure of the films prepared using a nitrogen flow ratio of 0.4 exhibited a crystalline cubic ZrN phase. The phase gradually changed to a mixture of crystalline ZrN and orthorhombic Zr₃N₄ followed by a Zr₃N₄ dominant phase as the N₂ flow ratio increased up to >0.5 and >0.85, respectively. The bonding characteristics of the ZrN_x films comprising Zr–N bonds of ZrN and Zr₃N₄ compounds were examined by X-ray photoelectron spectroscopy and were well correlated with the structural variation. With the formation of orthorhombic Zr₃N₄, the nanoindentation hardness and Young’s modulus levels of the ZrN_x (x = 0.92–1.38) films exhibited insignificant variations ranging from 18.3 to 19.0 GPa and from 210 to 234 GPa, respectively.

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 3d_5/2 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.