Spectral Sampling of Boron Diffusion in Ni Alloys: Cr and Mo Effects on Bulk and Grain Boundary Transport

TL;DR

This paper introduces a spectral sampling framework to analyze how Cr and Mo solutes influence boron diffusion in Ni alloys, revealing their distinct effects on bulk and grain boundary transport, which explains observed segregation behaviors.

Contribution

The study develops a novel spectral sampling method to quantify and interpret solute effects on interstitial diffusion in complex alloys, linking atomic-scale interactions to macroscopic transport phenomena.

Findings

Cr preserves in-plane boron mobility but limits out-of-plane transport.

Mo significantly reduces overall boron diffusivity and out-of-plane mobility.

Cr facilitates rapid boron redistribution at interfaces, while Mo strongly anchors boron at grain boundaries.

Abstract

Understanding how light interstitials migrate in chemically complex alloys is essential for predicting defect dynamics and long-term stability. Here, we introduce a spectral sampling framework to quantify boron diffusion activation energies in Ni and demonstrate how substitutional solutes (Cr, Mo) reshape interstitial point defect transport in both the bulk and along crystallographic defects. In the bulk, boron migration energy distributions exhibit distinct modality tied to solute identity and spatial arrangement: both Cr and Mo raise barriers in symmetric cages but induce directional asymmetry in partially decorated environments. Extending this framework to a $\Sigma5\langle100\rangle{210}$ symmetric tilt grain boundary reveals solute-specific confinement effects. Cr preserves low-barrier in-plane mobility while suppressing out-of-plane transport, guiding boron into favorable midplane voids. Mo, by contrast, imposes an across-the-board reduction in boron mobility, suppressing average diffusivity by two additional orders of magnitude at 800 $^\circ$C and reducing out-of-plane transport by five orders of magnitude relative to Cr. Both elements promote segregation by producing negative segregation energies, but their roles diverge: Cr facilitates rapid redistribution and stabilization at interfacial sites, consistent with Cr-rich boride formation, while Mo creates deeper and more uniform segregation wells that strongly anchor boron. Together, these complementary behaviors explain the experimental prevalence of Cr- and Mo-rich borides at grain boundaries and carbide interfaces in Ni-based superalloys. More broadly, we establish spectral sampling as a transferable framework for interpreting diffusion in disordered alloys and for designing dopant strategies that control transport across complex interfaces.