The alkali-silica reaction (ASR) and internal sulfatic reaction (ISR), normally both referred as internal expansive reactions, are among the most common causes of concrete structures deterioration worldwide. These reactions, which could be present simultaneously, origin products those are responsible for expansive stresses in the cement-based building materials, leading to severe cracking and loss of strength. The reaction products are also often amorphous or badly crystallized, or even present in very low content that they are very difficult to identify by current analytical physico-chemical techniques. The main macroscopic evidence of these degradation phenomena in concrete structures are the superficial occurrence of map-cracking, pop-outs and exudates (figure 1). Nevertheless, these symptoms are not exclusive and enough to establish a correct diagnosis.