Chemistry[edit]

Typical crack pattern of the alkali-silica reaction (ASR). The gel exudations through the concrete cracks have a characteristic yellow color and a high pH.

The reaction can be compared to the pozzolanic reaction which would be catalysed by the undesirable presence of too high concentrations
of alkali hydroxides (NaOH and KOH) in the concrete. It is a mineral acid-base reaction between NaOH or KOH, calcium hydroxide, also
known as Portlandite, or (Ca(OH)2), and silicic acid (H4SiO4, or Si(OH)4). When complete and to simplify, this reaction can be schematically
represented as following:
Ca(OH)2 + H4SiO4 Ca2+ + H2SiO42 + 2 H2O CaH2SiO4 2 H2O

Catalysis of ASR by NaOH or KOH[edit]

However, the ASR reaction significantly differs from the pozzolanic reaction by the fact that it is catalysed by
soluble alkali hydroxides (NaOH/ KOH) at very high pH. It can be represented as follows using the classical geochemical notation for
fully hydrated dissolved silica (Si(OH)4or silicic acid: H4SiO4), but an older industrial notation also exists (H2SiO3, hemihydrated silica
(does not exist), by analogy with carbonic acid):
2 Na(OH) + H4SiO4 Na2H2SiO4 2 H2O
Na2H2SiO4 2 H2O + Ca(OH)2 CaH2SiO4 2 H2O + 2 NaOH
The sum, or the combination, of the two above mentioned reactions gives a general reaction resembling the pozzolanic
reaction, but it is important to keep in mind that this reaction is catalysed by the undesirable presence in cement, or other
concrete components, of soluble alkaline hydroxydes (NaOH / KOH) responsible for the dissolution of the silicic acid at high
pH:
Ca(OH)2 + H4SiO4 CaH2SiO4 2 H2O
Without the presence of NaOH or KOH responsible for a high pH (~13.5), the amorphous silica would not be
dissolved and the reaction would not evolve. Moreover, the soluble sodium or potassium silicate is very hygroscopic
and swells when it absorbs water. When the sodium silicate gel forms and swells inside a porous siliceous aggregate,
it first expands and occupies the free porosity. When this latter is completely filled, if the soluble but very viscous gel
cannot be easily expelled from the silica network, the hydraulic pressure raises inside the attacked aggregate and
leads to its fracturation. It is the hydro-mechanical expansion of the damaged siliceous aggregate surrounded by
calcium-rich hardened cement paste which is responsible pour the development of a network of cracks in concrete.
When the sodium silicate expelled from the aggregate encounters grains of portlandite present in the hardened
cement paste, an exchange between sodium and calcium cations occurs and hydrated calcium silicate (C-S-H)
precipitates with a concomitant release of NaOH. In its turn, the regenerated NaOH can react with the amorphous
silica aggregate leading to an increased production of soluble sodium silicate. When a continuous rim of C-S-H
completely envelops the external surface of the attacked siliceous aggregate, it behaves as a semi-permeable barrier
and hinders the expulsion of the viscous sodium silicate while allowing the NaOH / KOH to diffuse from the hardened
cement paste inside the aggregate. This selective barrier of C-S-H contributes to increase the hydraulic pressure
inside the aggregate and aggravates the cracking process. It is the expansion of the aggregates which damages
concrete in the alkali-silica reaction.
Portlandite (Ca(OH)2) represents the reserve of OH anions in the solid phase. As long as portlandite, or the siliceous
aggregates, has not become completely exhausted, the ASR reaction will continue. The alkali hydroxides are
continuously regenerated by the reaction of the sodium silicate with portlandite and thus represent the transmission
belt of the ASR reaction driving it to completeness. It is thus impossible to interrupt the ASR reaction. The only way to
avoid ASR in the presence of siliceous aggregates and water is to maintain the concentration of soluble alkali (NaOH
and KOH) at the lowest possible level in concrete, so that the catalysis mechanism becomes negligible.

Analogy with the soda lime carbonation[edit]

The alkali-silica reaction mechanism catalysed by a soluble strong base as NaOH or KOH in the presence of
Ca(OH)2 (alkalinity buffer present in the solid phase) can be compared with the carbonation process of soda lime.
The silicic acid (H2SiO3 or SiO2) is simply replaced in the reaction by the carbonic acid (H2CO3 or CO2).

(1) CO2 + 2 NaOH Na2CO3 + H2O (CO2 trapping by soluble NaOH)

(2) Na2CO3 + Ca(OH)2 CaCO3 + 2 NaOH (regeneration of NaOH)
sum (1+2) CO2 + Ca(OH)2 CaCO3 + H2O (global reaction)

In the presence of water or simply ambiant moisture, the strong bases, NaOH or KOH, readily dissolve in
their hydration water (hygroscopic substances, deliquescencephenomenon) and this greatly facilitates
the catalysis process because the reaction in aqueous solution occurs much faster than in the dry solid phase. The
moist NaOH impregnates the surface and the porosity of calcium hydroxide grains with a high specific surface area.
Soda lime is commonly used in closed-circuit diving rebreathers and in anesthesiasystems.

Mechanism of concrete deterioration[edit]

The mechanism of ASR causing the deterioration of concrete can thus be described in four steps as follows:

1. The very basic solution (NaOH / KOH) attacks the siliceous aggregates (silicic acid dissolution at high pH),
converting the poorly crystallised or amorphous silica to a soluble but very viscous alkali silicate gel (N-S-
H, K-S-H).
2. The consumption of NaOH / KOH by the dissolution reaction of amorphous silica decreases the pH of the
pore water of the hardened cement paste. This allows the dissolution of Ca(OH)2 (portandite) and
increases the concentration of Ca2+ ions into the cement pore water. Calcium ions then react with the
soluble sodium silicate gel to convert it into solid calcium silicate hydrates (C-S-H). The C-S-H forms a
continuous poorly permeable coating at the external surface of the aggregate.
3. The penetrated alkaline solution (NaOH / KOH) converts the remaining siliceous minerals into bulky
soluble alkali silicate gel. The resulting expansive pressure increases in the core of the aggregate.
4. The accumulated pressure cracks the aggregate and the surrounding cement paste when the pressure
exceeds the tolerance of the aggregate.[6]