Abstract

It is believed that the segregation of oversized dopant ions to grain boundaries in Al2O3 hinders grain‐boundary diffusion, thereby reducing the tensile creep rate in this system by ∼2–3 orders of magnitude. In order to explain this improvement in creep behavior, it is helpful to characterize both the effective cation and interstitial volumes at grain boundaries, because the relative openness of some boundary structures suggests a great accommodation of oversized ions. In this study, the boundary volume is determined by a spatially local Voronoi construction, which highlights cation (Al3+) substitutional sites as well as large interstitial voids. In particular, we examine the spatial distribution of free volume near grain boundaries and, in addition, the dependence of the driving force for segregation on misfit strain in doped Al2O3. We interpret our results in light of recent evidence that selective codoping can provide a more efficient means of filling available space near boundaries, thereby further enhancing creep resistance.

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