Alkali-Silica Reactivity: Mechanisms And Management

Introduction In the decades since silica gel was first identified in material exuding from cracked concrete, a great deal of research has been conducted regarding the chemical reactions between the alkalies found in portland cement and silica found in aggregates. The reaction is complex and one that is not yet completely predictable, especially from the point of view of developing specifications that are appropriate to all situations. This paper is not intended to be a rigorous review of the research findings but is an attempt to provide a simplified review of the mechanisms of the alkali-silica reaction (ASR), so that one can better understand the implications of the specifications, test results and effects on structures. In addition, the contractual relationships between the aggregate supplier and one of their major clients, the concrete supplier, will be examined with regard to the ASR. ASR basics Silica. Silica (silicon oxide) may exist in naturally occurring aggregates in various forms and in combination with a number of other elements. When the silica is completely crystalline, such as in quartz, it is chemically and mechanically stable. Quartz silica is impermeable and reacts only on the surface of the crystal, where the silicon and oxygen bonds are broken. Because the surface area per unit volume of most quartz is low, the reactivity is also low. Completely amorphous (noncrystalline) silica is, on the other hand, more porous and very reactive. The less "crystalline" the silica is in the aggregate, the more reactive. Silica that has melted and cooled quickly without recrystallizing, creating a glassy material (such as in certain volcanic aggregates), has a very low state of crystallization and will be much more reactive in an alkaline solution. Crystalline silica that has been transformed by heat and pressure may have a large quantity of strain energy stored in the crystal lattice. The presence of this higher energy will make the silica more likely to react. The "strained quartz" found in many metamorphic aggregates means that these aggregates are potentially susceptible to deleterious alkali silica reactivity, although the rate of reaction is typically much slower than with aggregates composed of or containing glassy or amorphous silicas. Another problem may exist with aggregates in which the silica is primarily crystalline. In aggregates such as chert, in which the silica exists as very fine crystals (i.e., crypto- or microcrystalline), the very high surface energies between the crystals contribute to alkali sensitivity. Therefore, the potential reactivity of an aggregate is seen to be a function of both the degree of crystallization of the silica in the aggregate and the amount of energy stored in the crystal structure, whether due to a large quantity of microcrystalline silica, a high strain energy stored in the crystals or some combination of these factors. The surface area per unit volume of the reactive silica will also affect the rate of reaction, because a larger surface area of reactive silica will have more opportunity to react. Obviously, the reactivity of the aggregate is also affected by the silica content. However, in this case, the results are not quite so obvious. A discussion of the effect of silica content will be postponed until after a discussion of the contribution of the cement paste. Paste characteristics. Hydrated portland cement is a very alkaline material with a pore solution pH typically in excess of 12. The alkaline environment of moist concrete provides an ideal place for noncrystalline or cryptocrystalline silica to react. However, not all alkalies are equal in their effects. Calcium compounds react with glassy silica to form calcium silicate hydrate, commonly abbreviated C-S-H a poorly crystalline material that can occur in several forms and chemical compositions. C-S-H was at one time called tobermorite gel, because it was chemically similar to the naturally occurring crystalline mineral tobermorite and because it had a gel-like (noncrystalline) structure when viewed under an optical microscope. The formation of C-S-H is the basis for both portland cement hydration and reaction with, for example, fly ash. C-S-H is relatively stable. Although drying will cause some shrinkage and rewetting will cause some expansion, the volume stability of the C-S-H is very good compared to the volume stability of most alkali silica gels. Alkali silica gels with high sodium contents, for example, are nonstable compared to C-S-H.