The hot forged Ti–6Al–4V alloy demonstrates well constructed microstructure and balanced mechanical properties, which promotes its wide application in aviation field. However, its relative poor resistance to wear and foreign object impact usually leads to the cumulative damage, causing sudden failure and serious accident. Laser shock peening (LSP) is a novel surface plastic deformation technique, which could strengthen the surface layer of components through gradient grain structure. Nevertheless, the specific mechanism of microstructure evolution and mechanical properties enhancement of LSP processed hot forged Ti–6Al–4V alloy is still obscure, and its corresponding explanation would help the wide application. In the present research, the hot forged Ti–6Al–4V alloy was processed by LSP to regulate its superficial microstructure and improve mechanical properties, helping to understand the inner mechanism. The results reveal that LSP could simultaneously result in the merging of ultrafine α-Ti grains and refinement of coarse α-Ti grains, which reconstruct the dual-size grain structure. The crystal tilting and transformation promoted by the generation and movement of dislocations benefit the merging of ultrafine grains. Due to the different slip systems in dual phases, β-Ti phases exhibit much greater response to slip under surface plastic deformation, which are enforced to deform and construct the shell structure by sliding and phase transformation, while the α-Ti phases act as the core to synergistically construct ‘core-shell’ like structure. The increase of LSP impact time promotes the well wrapping of the ‘core-shell’ like structure and strengthens it by abundant dislocations, which also forms the gradient grain structure from surface to inner. Since the microstructure regulation and crystal defects engineering, the LSP improves the surface damage resistance and mechanical properties of the hot forged Ti–6Al–4V alloy obviously. Such results indicate a new technology to increase the properties of the hot forged Ti–6Al–4V alloy component further.
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