Ag diffusion in SiC high-energy grain boundaries: kinetic Monte Carlo study with first-principle calculations

TL;DR

This study uses ab initio calculations and kinetic Monte Carlo simulations to investigate silver impurity diffusion in high-energy grain boundaries of silicon carbide, revealing fast diffusion pathways and potential implications for nuclear fuel behavior.

Contribution

It introduces a first-principles based kinetic Monte Carlo model to quantify Ag diffusion in amorphous SiC grain boundaries, highlighting the dominant diffusion mechanisms and comparing with experimental data.

Findings

Ag diffuses via interstitial mechanisms in amorphous SiC.

HEGBs are among the fastest paths for Ag diffusion in SiC.

Predicted diffusion coefficients align with ion-implantation measurements.

Abstract

The diffusion of silver (Ag) impurities in high energy grain boundaries (HEGBs) of cubic (3C) silicon carbide (SiC) is studied using an ab initio based kinetic Monte Carlo (kMC) model. This study assesses the hypothesis that the HEGB diffusion is responsible for Ag release in Tristructural-Isotropic fuel particles, and provides a specific example to increase understanding of impurity diffusion in highly disordered grain boundaries. The HEGB environment was modeled by an amorphous SiC. The structure and stability of Ag defects were calculated using density functional theory code. The defect energetics suggested that the fastest diffusion takes place via an interstitial mechanism in a-SiC. The formation energy of Ag interstitials and the kinetic resolved activation energies between them were well approximated with Gaussian distributions that were then sampled in the kMC. The diffusion of Ag was simulated with the effective medium model using kMC. At 1200-1600C, Ag in a HEGB is predicted to exhibit an Arrhenius type diffusion and with a diffusion prefactor and effective activation energy of (2.73+-1.09)*10-10 m2s-1 and 2.79+-0.18 eV, respectively. The comparison between HEGB results to other theoretical studies suggested not only that GB diffusion is predominant over bulk diffusion, but also that the HEGB is one of fastest grain boundary paths for Ag diffusion in SiC. The Ag diffusion coefficient in the HEGB shows a good agreement with ion-implantation measurements, but is 2-3 orders of magnitude lower than the diffusion coefficients extracted from integral release measurements. The discrepancy between GB diffusion and integral release measurements suggests that other contributions are responsible for the fast release of Ag in some experiments and we propose that these contributions may arise from radiation enhanced diffusion.