The rim zone of cement-based materials – Barrier or fast lane for chemical degradation?

Sophisticated evaluation models for the long-term stability of cement-based systems demand a precise knowledge of the mechanisms of deterioration reactions, particularly respecting a permanent exposure to aqueous environments. Commonly, insights into these mechanisms are deduced from long-term investigations. However, these chemical reactions start immediately after exposure to aggressive environments causing rapid changes of composition and structure. Consequently, properties of its rim zone change, which affects transport processes in aqueous solutions. In laboratory experiments, the influence of these surface processes on the stability of cement-based materials exposed to different chloride solutions was studied as a function of time and temperature. Analysis of compositional and structural changes beneath the surface reveal the role of crystalline covering layers for chemical resistance. Such layers are often described as protective barriers. However, these processes in the rim zone can accelerate chemical degradation and subsequently reduce the resilience of the cement-based materials to aggressive aqueous environments.