Role of Chlorides in Corrosion of Reinforcing Steel in Concrete

Chlorides have long been held responsible for the initiation and progression of the corrosion of reinforcing steels in concrete structures, with higher concentrations assumed to cause earlier and more severe subsequent reinforcement corrosion. However, extensive field observations and detailed experimental results show that, in well-compacted, low-permeability concretes, reinforcement corrosion often does not occur even in the presence of high concentrations of chlorides. If corrosion does occur, it has been observed as pitting (and crevice) corrosion primarily at air voids in the concrete at the steel–concrete interface. Herein, it is shown that this is consistent with thermodynamic principles (Pourbaix) for the pitting of steel in practical concretes with high pH and air voids, irrespective of chloride concentration. Any subsequent corrosion becomes inhibited, in part through the formation of corrosion products. The experimental observations also show that there is a separate, concurrent process of the dissolution of calcium hydroxide and its leaching from the concrete. The rate of dissolution is accelerated proportionally to the concentration of chlorides. This is the primary mechanism for longer-term reinforcement corrosion, eventually producing circum-neutral pH at the steel and thereby setting up the thermodynamics permitting general corrosion. The findings question the relevance of a critical chloride concentration as an indicator of the commencement of reinforcement corrosion. Concrete permeability, remaining alkali reserves (or pH), and physical observation of evidence of rust damage are better indicators.