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To investigate the corrosion protection mechanism of polyaniline (PANI) films on ferrous metals, this work presents preparation method of a separate protonated PANI film electrode and results of its open-circuit potential (OCP) in 0.5 M NaClO4 and 0.5 M Na2SO4 solutions with different pH and the galvanic interaction between the PANI film electrode and ferrous metals. X-ray photoelectron spectroscopy (XPS) shows the lower pH corresponds to higher protonation level of H+ in the film, and a more positive OCP of PANI film. The PANI film accelerated the corrosion of 20A carbon steel slightly with a PANI to steel area ratio less than 25: 1, while the PANI films maintained passivity for a ratio above to 25:1 for the 20A steel. For the coupling of 2Cr13 stainless steel/PANI, an equal area PANI film could maintain 2Cr13 in a passive state. The results suggest that corrosion protection of 20A carbon steel and 2Cr13 stainless steel by PANI film in the acid solution is due to passivity protection. The excess oxidative charge stored in the PANI and the equilibrium activity of protonated PANI with the acid environment provide a persistent driving force for carbon steel and 2Cr13 stainless steel passivity. (C) 2004 Elsevier Ltd. All rights reserved.