Interstitial Solute Segregation at Triple Junctions: Implications for the Hydrogen Storage Properties of Nanomaterials

Abstract: At very fine grain sizes, grain boundary segregation can deviate from conventional behavior due to triple junction effects. While this issue has been addressed in prior work for substitutional alloys, here we develop a framework that accounts for interstitial sites in the grains, grain boundaries, and triple junctions of model Pd(H) polycrystals. This approach allows computation of interstitial segregation spectra separately at both defect types, which permits an understanding of segregation at all grain sizes via a size-scaling spectral isotherm. The size dependencies of dilute Pd(H) are found to be influenced not only by the triple junction content, but also by grain size-dependent lattice strains; the latter effect is evidenced by size dependencies of individual grain boundary and junction subspectra. The framework proposed here is applicable to interstitial alloys in general, and may serve as a basis for interfacial engineering in interstitial nanocrystalline alloys. As an example, we show using the dilute limit isotherm that hydrogen density can triple in nanocrystalline vis-`a-vis microcrystalline Pd due to hydrogen adsorption at intergranular defect sites.