Improving the high-temperature oxidation resistance of TiB2 thin films by alloying with Al

Refractory transition-metal diborides (TMB2) are candidates for extreme environments due to melting points above 3000 °C, excellent hardness, good chemical stability, and thermal and electrical conductivity. However, they typically suffer from rapid high-temperature oxidation. Here, we study the effect of Al addition on the oxidation properties of sputter-deposited TiB2-rich Ti1-xAlxBy thin films and demonstrate that alloying the films with Al significantly increases the oxidation resistance with a slight decrease in hardness. TiB2.4 layers are deposited by dc magnetron sputtering (DCMS) from a TiB2 target, while Ti1-xAlxBy alloy films are grown by hybrid high-power impulse and dc magnetron co-sputtering (Al-HiPIMS/TiB2-DCMS). All as-deposited films exhibit columnar structure. The column boundaries of TiB2.4 are B-rich, while Ti0.68Al0.32B1.35 alloys have Ti-rich columns surrounded by a Ti1-xAlxBy tissue phase which is predominantly Al rich. Air-annealing TiB2.4 at temperatures above 500 °C leads to the formation of oxide scales that do not contain B and mostly consist of a rutile-TiO2 (s) phase. The resulting oxidation products are highly porous due to the evaporation of B2O3 (g) phase as well as the coarsening of TiO2 crystallites. This poor oxidation resistance is significantly improved by alloying with Al. While air-annealing at 800 °C for 0.5 h results in the formation of an ~1900-nm oxide scale on TiB2.4, the thickness of the scale formed on the Ti0.68Al0.32B1.35 alloys is ~470 nm. The enhanced oxidation resistance is attributed to the formation of a dense, protective Al-containing oxide scale that considerably decreases the oxygen diffusion rate by suppressing the oxide-crystallites coarsening.