Evolution of strengthening precipitates, including their types, sizes, volume fraction, and chemical compositions in Al-4.0Zn-1.8Mg-1.2Cu (at.%) alloy during artificial aging, were investigated using anomalous small-angle X-ray scattering (ASAXS), three-dimensional atom probe techniques (APT), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and density functional theory (DFT) calculation. Upon aging, Cu-containing clusters merge with adjacent clusters to form larger clusters, which then act as nucleation sites for GPη' zones. As aging proceeds, GPη' zones grow up to η'I metastable phase with seven atomic layers on {111}Al planes, and this process is controlled by diffusion of Mg atoms. Cu atoms have a low diffusion rate and do not participate into the growth of precipitates within the first 60mins of aging. As aging time increases, Cu atoms enter the η'I metastable phase, leading to a significant increase in Cu content and (Zn+Cu)/Mg ratio; η'I metastable phase grow, and after exceeding about 7nm, gradually transform into the η'II metastable phase with ten atomic layers by adding three new atomic layers at one side. GPη' zones, η'I metastable phase and η'II metastable phase have symmetric interface structures. The precipitation sequence during aging to peak state can be summarized as: atomic clusters → GPη' zones → η'I metastable phase → η'II metastable phase.
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