The electrochemical hydrogen sorption behaviour of Zr-Cu-Al-Ni metallic glasses : Special issue on hydrogen absorbing materials

Abstract

Amorphous Zr-Cu-Al-Ni alloys are of interest for hydrogenation studies because they consist of a combination of early and late transition metals. Potentiodynamic polarisation tests were conducted to investigate the cathodic hydrogen reduction reactions on the surface of melt-spun Zr 55 Cu 30 Al 10 Ni 5 and Zr 65 Cu 17.5 Al 7.5 Ni 10 ribbons. In the Tafel region, the electrodic desorption reaction is the rate-determining step which competes with the hydrogen absorption reaction. In the next polarisation region, the hydrogen reduction takes place under mass transfer-control. The ribbons are galvanostatically charged with hydrogen to different hydrogen-to-metal ratios in 0.1 mol/l NaOH solution. The rate of hydrogen absorption of the Zr 55 Cu 30 Al 10 Ni 5 alloy is higher than that of the Zr 65 Cu 17.5 Al 7.5 Ni 10 alloy, although the hydrogen discharge rate on the surface of the Zr 65 Cu 17.5 Al 7.5 Ni 10 alloy is higher. Upon charging the samples at room temperature to H/M = 1.3 using a low charging rate (-1 mA/cm 2 ), the X-ray diffraction pattern show the main peaks of a Zr-hydride and Cu and/or a Cu rich phase(s) besides the amorphous phase. The potentiostatic double-pulse technique (PDP) was applied to estimate the fraction of reversibly absorbed hydrogen in the amorphous alloy samples by charging at different cathodic potentials. Subsequently, the residual hydrogen concentration (irreversibly absorbed hydrogen) was determined by hot extraction. The Zr 55 Cu 30 Al 10 Ni 5 alloy was found to absorb a higher fraction of reversible hydrogen than the Zr 65 Cu 17.5 Al 7.5 Ni 10 alloy.