Reactive Element Effects in High-Temperature Alloys Disentangled

Reactive elements-REs-are decisive for the longevity of high-temperature alloys. This work joins several previous efforts to disentangle various RE effects in order to explain apparently contradicting experimental observations in alumina forming alloys. At 800-1000 degrees C, messy aluminum oxy-hydroxy-hydride transients initially formed due to oxidation by H2O which in turn undergo secondary oxidation by O-2. The formation of the transient oxide becomes supported by dispersed RE oxide particles acting as water equivalents. At higher temperatures, electron conductivity in impurity states owing to oxygen vacancies in grain boundaries (GBs) becomes increasingly relevant. These channels are subsequently closed by REs pinning the said vacancies. The universality of the emerging understanding is supported by a comparative first-principles study by means of density functional theory addressing RE(III): Sc2O3, Y2O3, and La2O3, and RE(IV): TiO2, ZrO2, and HfO2, that upon reaction with water, co-decorate a generic GB model by hydroxide and RE ions. At 100% RE coverage, the GB model becomes relevant at both temperature regimes. Based on reaction enthalpy Delta H-r considerations, messy aluminum oxy-hydroxy-hydride transients are accessed in both classes. Larger variations in Delta H-r are found for RE(III)-decorated alumina GBs as compared to RE(IV). For RE(III), correlation with GB width is found, increasing with increased ionic radius. Similarly, upon varying RE(IV), minor changes in stability correlate with minor structural variations. GB decorations by Ce(III) and Ce(IV) further consolidate the emerging understanding. The findings are used to discuss experimental observations that include impact of co-doping by RE(III) and RE(IV).