The superplastic tensile test was carried out on SP700 (Ti-4.5Al-3V-2Mo-2Fe) titanium alloy sheet at 760 °C by the method of maximum m value, and the microstructure characteristics were investigated to understand the deformation mechanism. The results indicated that the examined alloy showed an extremely fine grain size of ~1.3 μm and an excellent superplasticity with fracture elongation of up to 3000%. The grain size and the volume fraction of the β phase increased as the strain increased, accompanied by the elements’ diffusion. The β-stabilizing elements (Mo, Fe, and V) were mainly dissolved within the β phase and diffused from α to β phase furthermore during deformation. The increase in strain leads to the accumulation of dislocations, which results in the increase in the proportion of low angle grain boundaries by 15%. As the deformation process, the crystal of α grains rotated, and the texture changed, accompanied by the accumulation of dislocations. The phase boundary (α/β) sliding accommodated by dislocation slip was the predominant mechanism for SP700 alloy during superplastic deformation.

The fracture-behaviors of two Ti-Al-Sn-Zr-Mo-Nb-W-Si alloys with different slow-diffusing β stabilizing elements (Mo, W) were investigated through in-situ tensile testing at 650 °C via scanning electron microscopy. These alloys have two phases: the α phase with hcp-structure (a = 0.295 nm, c = 0.468 nm) and the β phase with bcc-structure (a = 0.332 nm). Three-dimensional atom probe (3DAP) results show that Mo and W mainly dissolve in the β phase, and they tend to cluster near the α/β phase boundary. Adding more slow-diffusing β stabilizing elements can improve the ultimate tensile strength and elongation of the alloy at 650 °C. During tensile deformation at 650 °C, microvoids mainly initiate at α/β interfaces. With increases in the contents of Mo and W, the β phase content increases and the average phase size decreases, which together have excellent accommodative deformation capability and will inhibit the microvoids’ nucleation along the interface. In addition, the segregation of Mo and W near the α/β interface can reduce the diffusion coefficient of the interface and inhibit the growth of microvoids along the interface, which are both helpful to improve the ultimate tensile strength and plasticity.