The film forming kinetics and reaction mechanism of gamma-GPS on low carbon steel surfaces was investigated by FTIR-ATR, AFM, NSS and theoretical calculation method. The results from experimental section indicated that the reaction of gamma-GPS on low carbon steel surfaces followed the conventional reaction mechanism, which can be described as reaction (I) (Me (Metal)-OH + HO-Si -> Me-O-Si + H2O) and reaction (II) (Si-OH + Si-OH -> Si-O-Si + H2O). During film forming process, the formation of Si-O-Fe bond (reaction (I)) exhibited oscillatory phenomenon, the condensation degree of silanol monomers (reaction (II)) increased continuously. The metal hydroxyl density had significant influence on the growth mechanisms and corrosion resisting property of gamma-GPS films. The results from theoretical calculation section indicated that the patterns of reaction (I) and reaction (II) were similar, involving a nucleophilic attack on the silicon center. The formation of Si-O-Fe bond (reaction (I)) was kinetically and thermodynamically preferred, which had catalytic effect on its condensation with neighboring silanol monomers (reaction (II)). Our DFT calculations were good consistent with the experimental measurements. (C) 2010 Elsevier B.V. All rights reserved.