This work presents a theoretical assessment of galvanic (relative) nobility of four intermetallic particles (IMPs), Al 2 Cu, Al 2 CuMg, Mg 2 Si and MgZn 2 , in aluminum alloys through work function calculation based on density functional theory (DFT). The concepts of work function, Volta potential and relative nobility are discussed with respect to the IMPs and aluminum matrix. The calculated Volta potentials are compared with reported experimental Volta potentials measured by scanning Kelvin probe force microscopy (SKPFM). Various crystal faces and terminal types are examined in the DFT calculation, showing that these two factors have a significant effect on the work function value. Considering the large divergence in the reported experimental data, the comparison shows a general agreement between the calculated and experimental Volta potential data for the investigated IMPs. The DFT calculations provide theoretical explanations for several experimental phenomena. The results demonstrate that DFT calculation is a valuable theoretical approach for assessment of the relative nobility of different phases in the alloys, providing complementary information to experimental data from SKFPM. Moreover, the implications of the calculated Volta potentials are discussed with respect to the corrosion potentials. The addition of various alloying elements into the aluminum (Al) matrix to improve mechanical performance of Al alloys may simultaneously increase their susceptibility to localized corrosion. This is mainly due formation of intermetallic particles (IMPs) that may trigger micro-galvanic corrosion along the interface between the IMPs and the alloy matrix.1 The potential differences between the IMPs and the matrix may result in localized dissolution of the matrix or dealloying of the IMP.
2The most common IMPs present in 2xxx and 7xxx series Al alloys include Al 2 CuMg (S-phase), Al 2 Cu (θ-phase), Al 7 Cu 2 Fe (β-phase), MgZn 2 (η-phase) and Mg 2 Si.3-5 IMPs containing Cu and Fe, such as Al 2 Cu. 6 and Al 7 Cu 2 Fe, 7 are considered to be cathodic with respect to the matrix, acting as local cathodes and thus promoting cathodic reactions such as oxygen reduction. In contrast, Mg-rich IMPs, such as Al 2 CuMg, are considered anodic relative to the matrix, resulting in selective dissolution and concomitant Cu-enrichment of the IMP.8 These localized corrosion events may eventually trigger other corrosion forms, such as stress corrosion cracking or intergranular corrosion.9 Therefore, micro-galvanic corrosion effects between IMPs and the Al matrix is considered to be of utmost importance for the overall service performance of Al alloys.In 1987, Stratmann started to use the Kelvin probe to investigate corrosion properties of metals under thin electrolyte films.10 His measurements revealed a linear relationship between Volta potential and corrosion potential of Cu, Zn, Fe and other metals. Later, the scanning Kelvin microprobe was developed and used for Volta potential measurements of several metals in humid atmospheres.11 Du...
