Understanding the strengthening effect of niobium on ferrite grain boundaries from the perspective of valence electron structures will help to use niobium and other microalloying elements more effectively to improve the performance of steel materials. In this paper, the effect of niobium element on ferrite grain boundary strengthening is studied based on microstructure analysis at the nanometer scale. The enrichment of niobium in pipeline steel at ferrite boundary was observed by a three-dimensional atomic probe test. Segregation of Nb is observed in the ferrite grain boundaries of X70 steel, and its maximum concentration is 0.294-0.466 at.%. The charges in the occupancy of the Fe 3d state in grain and grain boundary were 7.23 and 7.37, respectively, based on quantitative analysis of electron energy loss spectra (EELS). The first-principle calculation suggests that the charges in the occupancy of 3d state for grain boundary iron are 6.57 and 6.68, respectively, before and after the Nb doping (with an increase of 1.67%), which reveals a similar trend to that of the EELS results. Through Nb alloying, the 3d valence electronic density of the state of Fe in grain boundary moves to a lower energy, which can reduce the total energy of the system and make the grain boundary more stable. Meanwhile, the charges in the occupancy of the 3d state for Fe in the grain boundary increases, providing more electrons for grain boundary bonding. These improve the strength and toughness of the material. This work provides a fundamental understanding for pipeline steel strengthening by element alloying.
Keywords: 3D atom probe; electron energy loss spectrum; first principles; grain boundary; valence electron structure.