Long-term prediction of reinforced concrete structures - Use of thermodynamic data to assess steel corrosion in carbonated concrete

In the context of the prediction of the long-term behaviour of reinforced concrete structures involved in the nuclear waste storage, the corrosion mechanisms of the steels have to be assessed and modelled. When nuclear wastes are embedded in reinforced concrete containers, the chemical environment of the reinforcement is progressively modified, due to the diffusion of the carbonation front inside the concrete matrix. This modification leads to the variation of the properties of the iron oxides formed at the steel/concrete interface, and the active corrosion can be initiated. In order to understand and modelled the mechanisms of steel corrosion in concrete, the equilibrium of two main systems must be separately described with the help of thermodynamic data issued from the literature: - The mineral phases, lime and calcium silicate hydrate (C-S-H), in equilibrium with the pore solution during the propagation of the carbonation front; - The iron oxides in equilibrium with the aqueous solution. For this purpose, the nature of aqueous species present in the pore solution was calculated in the whole range of pH encountered during the cement paste degradation by carbonation. As a matter of fact, as the pH decreases, calcium concentration decreases and silicates concentration increases due to the calcium carbonate formation and C-S-H dissolution. The pH of a carbonated concrete ranges between 8.3 and 10, depending on the partial pressure of carbon dioxide in the porosity and the conversion degree of carbonation. In this pH range, the iron oxides equilibria were analysed as a function of the redox potential and aqueous species (carbonates and sulphates present in the solution) present inside the solution. In a reductive solution and in presence of carbonates, the high solubility of iron oxides may prevent passivation or generate the dissolution of the passive film. Moreover, the relevance of thermodynamics calculations has been confirmed by corrosion tests of mild steel immersed in solutions containing carbonates, in the pH range 8.3 to 10. (authors)