Abstract
Grain boundaries (GBs) trigger structure-specific chemical segregation of solute atoms. According to the three-dimensional (3D) topology of grains, GBs - although defined as two-dimensional defects - cannot practically be free of curvature. This leads to discrete variations in the GB plane orientations. Topologically required arrays of secondary GB dislocations accommodate these variations as well as deviations from ideal coincidence site lattice GBs. We report here that these pattern-forming secondary GB dislocations can have an additional and, in some cases, even a much stronger effect on GB segregation than defect-free GBs. Using nanoscale correlative tomography combining crystallography and chemical analysis, we quantified the relationship between secondary GB dislocations and their segregation energy spectra for a model Fe-W alloy. This discovery unlocks design opportunities for advanced materials, leveraging the additional degrees of freedom provided by topologically-necessary secondary GB dislocations to modulate segregation.