Interstitial diffusion of hydrogen in M7C3 (M=Cr,Mn,Fe)

To increase the understanding of the role of carbide precipitates on the hydrogen embrittlement of martensitic steels, we have performed a density functional theory study on the solution energies and energy barriers for hydrogen diffusion in orthorhombic M7C3 (M = Cr, Mn, Fe). Hydrogen can easily diffuse into the lattice and cause internal stresses or bond weakening, which may promote reduced ductility. Solution energies of hydrogen at different lattice positions have systematically been explored, and the lowest values are-0.28, 0.00, and 0.03 eV/H-atom for Cr7C3, Mn7C3, and Fe7C3, respectively. Energy barriers for the diffusion of hydrogen atoms have been probed with the nudged elastic band method, which shows comparably low barriers for transport via interstitial octahedral sites for all three systems. Analysis of the atomic volume reveals a correlation between low solution energies and energy barriers and atoms with large atomic volumes. Furthermore, it shows that the presence of carbon tends to increase the energy barrier. Our results can explain previous experimental findings of hydrogen located in the bulk of Cr7C3 precipitates and provide a solid basis for future design efforts of steels with high strength and commensurable ductility.

Automated summary

To understand the impact of carbide precipitates on martensitic steels' hydrogen embrittlement, we used density functional theory to investigate the solution energies and energy barriers for hydrogen diffusion in orthorhombic M7C3 (M = Cr, Mn, Fe). Our findings reveal that hydrogen diffuses easily into the lattice, leading to internal stresses or weakened bonds, ultimately reducing ductility. The lowest hydrogen solution energies were found to be-0.28, 0.00, and 0.03 eV/H-atom for Cr7C3, Mn7C3, and Fe7C3, respectively. The nudged elastic band method showed relatively low energy barriers for hydrogen diffusion via interstitial octahedral sites. Analysis of atomic volumes showed a correlation between low solution energies and energy barriers and atoms with large atomic volumes, with the presence of carbon increasing the energy barrier. These results explain previous experimental observations of hydrogen in the bulk of Cr7C3 precipitates and provide a solid foundation for future steel design with high strength and commensurable ductility.