Role of late transition metals on pitting resistance of Zr-Ti-(Cu,Ni,Co)-Al bulk metallic glasses in 0.6 M NaCl aqueous solution

Four quanternary Zr-based bulk metallic glasses(BMGs)were selected,including the Zr_(46)Ti_2Cu_(45)Al_7,Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15),due to their robust glass-forming ability and containing a single species of late transition metal(LTM)in compositions.Their pitting resistances in 0.6 M Na Cl aqueous solution were investigated to examine the role of LTM elements in the alloys,with electrochemical measurements,surface morphology observation and x-ray photoelectron spectrometry analysis.It is shown that in comparision with two Cu-bearing BMGs,Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs exhibited significantly superior resistance to pitting.Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs manifested distinct passivation behaviour,because of the formation of surface passive film mainly comprising of Zr O_2,Ti O_2and Al_2O_3.However,no significant differences in the electrochemical resistive properties and thicknesses of passive films were found between Zr_(61)Ti_2Cu_(25)Al_(12)and Zr_(55)Ti_4Ni_(22)Al_(19)BMGs.Nevertheless,at the passive film/metal interface,copper enrichment took place in Zr_(61)Ti_2Cu_(25)Al_(12),whereas the nickel was slightly deficient at the interface in Zr_(55)Ti_4Ni_(22)Al_(19).During pitting propagation,selective dissolution of the zirconium,titanium and aluminum over the copper took place in Zr_(61)Ti_2Cu_(25)Al_(12),but it was not the case in Zr_(55)Ti_4Ni_(22)Al_(19).For the two Cu-bearing BMGs,reduction of passive base metal elements in composition resulted in local selective dissolution,even absence of the passivation.