Microstructure and hydrogen storage properties of non-stoichiometric Zr–Ti–V Laves phase alloys

The non-stoichiometric C15 Laves phase alloys namely Zr0.9Ti0.1Vx (x = 1.7, 1.8, 1.9, 2.1, 2.2, 2.3) are designed and expected to investigate the role of defect and microstructure on hydrogenation kinetics of AB2 type Zr-based alloys. The alloys are prepared by non-consumable arc melting in argon atmosphere and annealed at 1273 K for 168 h to ensure the homogeneity. The microstructure and phase constitute of these alloys are examined by SEM, TEM and XRD. The results indicate the homogenizing can reduce the minor phases α-Zr and abundant V solid solution originating from the non-equilibrium solidification of as-cast alloys. Twin defects with {111}<011 > orientation relationship are observed, and the role of defects on hydrogenation kinetics is discussed. Hydrogen absorption PCT characteristics and hydrogenation kinetics of Zr0.9Ti0.1Vx at 673–823 K are investigated by the pressure reduction method using a Sievert apparatus. The results show the hypo-stoichiometric alloys preserve faster hydrogenation kinetics than the hyper-stoichiometric ones due to the decrease of dendritic V. The excess content of Zr3V3O phase decreases the hydrogenation kinetics and the stability of hydrides. In addition, the different rate controlled mechanisms during hydrogen absorption are analyzed. The effects of non-stoichiometry on the crystal structure and hydrogen storage properties of Zr0.9Ti0.1Vx Laves alloys are discussed.