Additive manufacturing of Inconel 625 components attracts great interest due to its ability to produce parts with complex geometries that are needed for high-temperature applications in the aerospace, energy, automotive and chemical industries. To take full advantage of the potential of additive manufacturing, an in-depth understanding of the effects of prolonged high-temperature annealing on microstructure and hardness evolution is needed. Previous research in this field has mainly focused on a limited range of temperature and time. This study aims to determine the effect of prolonged high-temperature annealing on the evolution of intermetallic phases and carbides, as well as changes in the dislocation substructure of Inconel 625 superalloy additively manufactured by laser powder bed fusion subjected to stress relief annealing and subsequent isothermal annealing at a temperature up to 800 °C for 5–500 h. The microstructure development is correlated with hardness behaviour. It is determined that the microstructure evolution proceeds in four stages with temperature and time increase. In the initial stress-relieved condition, a cellular microstructure with nano-sized precipitates of the Laves phase and NbC carbides at the cell walls occurs, and hardness is equal to 300 HV10. In the 1st stage of the microstructure evolution, the γ'' phase particles precipitate on the cell walls, which results in hardening up to 383 HV10 in the specimen annealed at 700 °C for 5 h. The 2nd stage involves the precipitation of the γ'' phase both on the cell walls and inside the cells, as well as the formation of dislocation networks, which contribute to the softening effect and hardness drop to 319 HV10. In the 3rd stage, at temperature 700 and 800 °C, the δ phase, M23C6 carbides, and the Laves phase precipitate and grow, and the subgrain boundaries are formed. The hardness is in the range of 340–350 HV10 and is higher than in the 2nd stage. In the 4th stage, as the annealing time is increased at a temperature of 800 °C, the δ phase and M23C6 carbides coagulate, and the Laves phase particles spheroidize or partially dissolve. Very intense precipitation and growth of the hard δ phase particles provide an increase in hardness to 402 HV10. As a result of systematic studies, the various strengthening and softening mechanisms acting during high-temperature annealing are determined.
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