This study elucidated the effect of Ti–Mo microalloying on the hydrogen embrittlement (HE) resistance and fracture behavior of warm-rolled Fe-5.6Mn-0.16C-1Al (wt%) steel. After intercritical annealing, both steels, i.e., without and with Ti–Mo microalloying, showed ultrafine ferrite (
α) and austenite (
γ
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This study elucidated the effect of Ti–Mo microalloying on the hydrogen embrittlement (HE) resistance and fracture behavior of warm-rolled Fe-5.6Mn-0.16C-1Al (wt%) steel. After intercritical annealing, both steels, i.e., without and with Ti–Mo microalloying, showed ultrafine ferrite (
α) and austenite (
γR) duplex microstructure. The addition of Ti–Mo to 5.6Mn steel reduces the volume fraction of
γR, facilitating the formation of (Ti, Mo)C carbides in
α phase and further refining the final microstructure. The product of ultimate tensile strength (UTS) and total elongation (TEL) of 5.6MnTiMo can be as high as 35 GPa·% with an ultra-high yield strength of above 1.2 GPa. Furthermore, the addition of Ti–Mo also had a significant effect on the resistance to HE of medium Mn steels. Firstly, the limited (Ti, Mo)C carbides precipitated in
γR could act as irreversibly trap sites to capture a considerable amount of H, effectively increasing the C
H (Diffusible Hydrogen Content). Additionally, 5.6MnTiMo displayed higher
γR stability, resulting in a reduced susceptibility to HE. The H-assisted microcracks mainly formed inside
γ(
α′) and extended along
γ(
α′) grain boundaries, leading to intergranular cracking and premature fracture.
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