Electrochimica Acta 46 (2001) 1339 – 1358 Influence of molybdenum on the conduction mechanism in passive films on iron – chromium alloys in sulphuric acid solution Martin Bojinov a, *, Gunilla Fabricius b , Timo Laitinen a,1 , Kari Ma ¨kela ¨ a , Timo Saario a , Go ¨ ran Sundholm b,1 a VTT Manufacturing Technology, PO Box 1704, FIN-02044 VTT, Espoo, Finland b Laboratory of Physical Chemistry and Electrochemistry, Helsinki Uniersity of Technology, PO Box 6100, FIN-02015 HUT, Espoo, Finland Received 28 September 2000; received in revised form 26 October 2000 Abstract This paper describes an extension of the mixed-conduction model to predict quantitatively the electrochemical behaviour and transport properties of anodic films on pure Cr, Fe–Cr alloys and Fe–Cr–Mo alloys in 1 M sulphuric acid solution. The anodic films on Fe–Cr–Mo alloys (12 and 25% Cr; 0, 5 and 10% Mo) were studied using rotating ring-disk voltammetry, impedance spectroscopy and resistance measurements. The addition of Mo to the Fe – Cr alloys was found to decrease the resistance of the film both in the passive and transpassive region. During the re-activation of the Fe–12%Cr– x %Mo alloys at negative potentials, soluble products were found to be released at a higher potential than during the re-activation of the Fe – 12%Cr alloy. Re-activation proceeds to a lesser extent for the Fe–25%Cr alloy, and was not observed for the Fe–25%Cr– x %Mo alloys. The addition of Mo was also found to lead to a marked increase of the transpassive dissolution rate of the alloys. The impedance spectroscopic results indicated that the addition of Mo increases the rate of the interfacial generation of positive defects and especially annihilation of negative defects. The present extension of the mixed-conduction model for anodic passive films was found to describe quantitatively the resistance and impedance spectroscopic data for Fe – 25%Cr and Fe – 25%Cr – 10%Mo alloy, as well as earlier data on pure Cr. The same kinetic model can be used to describe the behaviour of the films on all these materials. It is thus most likely that a Cr-oxide-based film is formed which determines the behaviour of the Fe–25%Cr and Fe–25%Cr–10%Mo alloys as well. © 2001 Elsevier Science Ltd. All rights reserved. Keywords: Iron – chromium – molybdenum alloys; Impedance spectroscopy; Contact electric resistance technique; Kinetic model; Ionic and electronic conductivity www.elsevier.nl/locate/electacta 1. Introduction The anodic films on iron, chromium and Fe–Cr alloys have a nanocrystalline structure which resembles that of the corresponding bulk oxides [1–4]. This infor- mation is based on recent applications of advanced in-situ surface analytical techniques. On the other hand, ex-situ techniques such as XPS and STM have shown * Corresponding author. Tel.: +358-9-4565873; fax: +358- 9-4565875. E-mail address: martin.bojinov@vtt.fi (M. Bojinov). 1 ISE member. 0013-4686/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved. PII:S0013-4686(00)00713-1