High- and medium-entropy nitride coatings from the Cr-Hf-Mo-Ta-W-N system: properties and high-temperature stability

Abstract

High- and medium-entropy nitride coatings from the Cr-Hf-Mo-Ta-W-N system were studied using ab initio calculations and experiments to clarify the role of entropy and individual elements in phase stability, microstructure, and high-temperature behaviour. Formation energy calculations indicated that nitrogen vacancies stabilise the cubic (fcc) phase, with hafnium and tantalum acting as strong stabilisers, while tungsten destabilises the lattice. Coatings were deposited by reactive magnetron sputtering at approx. 50C (AT) and approx. 580C (HT). All exhibited columnar fcc structures; high-temperature deposition produced denser coatings, lower nitrogen content, and larger crystallites, resulting in higher hardness and elastic modulus. Thermal stability was tested up to 1200C on Si and oxidation at 1400C on sapphire. AT coatings failed early, while most HT coatings endured. Nitrogen loss less than 10 at.% at 1000C was critical for survival. TEM revealed tungsten segregation and HfO2 formation, while fcc nitride remained dominant. Ta enrichment proved essential for superior thermal and oxidation stability.