the electochemistry of corrosion cut（腐蚀的electochemistry削减）.pdf

THE ELECTROCHEMISTRY OF CORROSION Edited by Gareth Hinds from the original work of J G N Thomas INTRODUCTION The surfaces of all metals (except for gold) in air are covered with oxide films. When such a metal is immersed in an aqueous solution, the oxide film tends to dissolve. If the solution is acidic, the oxide film may dissolve completely leaving a bare metal surface, which is said to be in the active state. In near-neutral solutions, the solubility of the oxide will be much lower than in acid solution and the extent of dissolution will tend to be smaller. The underlying metal may then become exposed initially only at localised points where owing to some discontinuity in the metal, e.g. the presence of an inclusion or a grain boundary, the oxide film may be thinner or more prone to dissolution than elsewhere. If the near-neutral solution contains inhibiting anions, this dissolution of the oxide film may be suppressed and the oxide film stabilised to form a passivating oxide film which can effectively prevent the corrosion of the metal, which is then in the passive state. When the oxide-free surface of a metal becomes exposed to the solution, positively charged metal ions tend to pass from the metal into the solution, leaving electrons behind on the metal, i.e. M → M n+ + ne− (1) atom in metal surface ion in solution electron(s) in metal The accumulation of negative charge on the metal due to the residual electrons leads to an increase in the potential difference between the metal and the solution. This potential difference is called the electrod