Superior oxidation resistance of the chemically complex but structurally simple Ti-Al-Ta-Ce-Si-La-B-nitride

Abstract

Alloying (Ti,Al)N with Ta, CeSi2 or LaB6 is beneficial for both hardness and thermal stability. Here we show that their different mechanisms allow for a cumulative improvement when alloyed together, which is especially pronounced for the oxidation resistance. During isothermal oxidation treatments in ambient air at 900 °C (for up to 25 h), Ti0.44Al0.44Ta0.12N allows for a parabolic scale growth rate constant kp of 6.039 × 10-5 µm2/s. This is reduced to 2.074 × 10-5 and even 0.399 × 10-5 µm2/s when alloying with 2 mol% CeSi2 respectively CeSi2 + LaB6 (1 mol% each). The oxide scale growth kinetics for the latter can be even better described by a logarithmic or cubic law. In the as-deposited state the CeSi2 and CeSi2 + LaB6 alloyed (Ti,Al,Ta)N are single-phase fcc structured providing an indentation hardness of 32.6 ± 1.5 and 37.8 ± 1.5 GPa, combined with an indentation modulus of 496 ± 22 and 496 ± 14 GPa, respectively. After vacuum-annealing at 1000 °C, their hardness is still 33.0 ± 1.6 and 34.8 ± 1.1 GPa, and noticeable formation of hexagonal AlN and TaNx phases can only be detected by X-ray diffraction when annealed at temperatures above 1200 °C. Using CeSi2 and LaB6 instead of their elemental form is furthermore beneficial for the target production itself, as Ce and La are highly reactive.