Conventional metals become harder with decreasing grain sizes, following the classical Hall-Petch relationship. However, this relationship fails and softening occurs at some grain sizes in the nanometer regime for some alloys. In this study, we discovered that plastic deformation mechanism of extremely fine nanograined metals and their hardness are adjustable through tailoring grain boundary (GB) stability. The electrodeposited nanograined nickel-molybdenum (Ni-Mo) samples become softened for grain sizes below 10 nanometers because of GB-mediated processes. With GB stabilization through relaxation and Mo segregation, ultrahigh hardness is achieved in the nanograined samples with a plastic deformation mechanism dominated by generation of extended partial dislocations. Grain boundary stability provides an alternative dimension, in addition to grain size, for producing novel nanograined metals with extraordinary properties.

Grain boundaries in ultrafine grained (UFG) materials processed by severe plastic deformation (SPD) are often called "non-equilibrium" grain boundaries. Such boundaries are characterized by excess grain boundary energy, presence of long range elastic stresses and enhanced free volumes. These features and related phenomena (diffusion, segregation, etc.) have been the object of intense studies and the obtained results provide convincing evidence of the importance of a non-equilibrium state of high angle grain boundaries for UFG materials with unusual properties. The aims of the present paper are first to give a short overview of this research field and then to consider tangled, yet unclear issues and outline the ways of oncoming studies. A special emphasis is given on the specific structure of grain boundaries in ultrafine grained materials processed by SPD, on grain boundary segregation, on interfacial mixing linked to heterophase boundaries and on grain boundary diffusion. The connection between these unique features and the mechanical properties or the thermal stability of the ultrafine grained alloys is also discussed.