Effect of Niobium on the Electronic Properties of Passive Films on Zirconium Alloys

The effects of Niobium on the structure and properties(especially electric properties) of passive film of Zirconium alloys in pH 8.5 buffer solution are examined by the photo-electrochemical analysis. For Zr-xNb alloys (x = 0, 0.45, 1.5, 2.5 wt%), photocurrent began to increase at the incident energy of 3.5 ~ 3.7 eV and exhibited the $1^{st}$ peak at 4.3 eV and the $2^{nd}$ peak at 5.7 eV. From $(i_{ph}hv)^{1/2}$ vs. hv plot, indirect band gap energies $E_g{^1}$= 3.01~3.47 eV, $E_g{^2}$= 4.44~4.91 eV were obtained. With increasing Nb content, the relative photocurrent intensity of $1^{st}$ peak significantly increased. Compared with photocurrent spectrum of thermal oxide of Zr-2.5Nb, It was revealed that $1^{st}$ peak in photocurrent spectrum for the passive film formed on Zr-Nb alloy was generated by two types of electron transitions; the one caused by hydrous $ZrO_2$ and the other created by Nb. Two electron transition sources were overlapped over the same range of incident photon energy. In the photocurrent spectrum for passive film formed on Zr-2.5Nb alloy in which Nb is dissolved into matrix by quenching, the relative photocurrent intensity of $1^{st}$ peak increased, which implies that dissolved Nb act as another electron transition source.