Prediction and hydrogen acceleration of ordering in iron-vanadium alloys

Ab initio calculations of binary metallic systems often predict ordered compounds in contrast to empirical reports of solid solutions or disordered phases. These discrepancies are usually attributed to slow kinetics that retains metastable structures at low temperatures. The Fe-V system is an example of this phenomenon, in which we predict two ordered stable ground states, Fe3V and FeV3, whereas a disordered σ phase is reported. We propose to overcome this difficulty by hydrogen absorption, which facilitates metal atom mobility through vacancy formation and separation between the two elements due to their opposite affinities towards it, thus accelerating transformation kinetics. Hydrogen also increases the relative stability of the ordered structures compared with that of the σ phase without affecting the shape of the phase diagram. The hydrogen-induced formation of the ordered structures is expressed by a reversible decrease of the electrical resistivity with increasing hydrogen pressure. Such behavior has not been reported before in thin H absorbing films. Formation of the ordered structures is further substantiated by the kinetics of the resistivity changes upon variation of the hydrogen pressure, where two stages are distinguished: a fast initial stage and a much slower subsequent process in which the resistivity changes direction, associated with hydrogen dissolution and phase transformation, respectively.