Routes to control diffusive pathways and thermal expansion in Ti-alloys

β-stabilized Ti-alloys present several unexplored and intriguing surprises in relation to orthorhombic α″ phases. Among them are (i) the diffusion-controlled formation of transitional α″_iso, α″_lean and α″_rich phases and ii) the highly anisotropic thermal expansion of martensitic α″. Using the prototypical Ti-Nb system, we demonstrate that the thermodynamic energy landscape reveals formation pathways for the diffusional forms of α″ and may lead to a stable β-phase miscibility gap. In this way, we derive temperature-composition criteria for the occurrence of α″_iso and resolve reaction sequences during thermal cycling. Moreover, we show that the thermal expansion anisotropy of martensitic α″ gives rise to directions of zero thermal strain depending on Nb content. Utilizing this knowledge, we propose processing routes to achieve null linear expansion in α″ containing Ti-alloys. These concepts are expected to be transferable to other Ti-alloys and offer new avenues for their tailoring and technological exploitation.