Alkali–silica reaction

From Wikipedia, the free encyclopedia

Characteristic crack pattern associated with the alkali–silica reaction affecting a concrete step barrier on a
US motorway[1][2]

For less common types of alkali-driven concrete degradation, see Alkali-aggregate reaction.
The alkali–silica reaction (ASR), more commonly known as "concrete cancer", is a swelling
reaction that occurs over time in concrete between the highly alkaline cement paste and the
reactive non-crystalline (amorphous) silica found in many common aggregates, given sufficient
moisture. The expansion of concrete through reaction between cement and aggregates was first
studied by Thomas E. Stanton in California during the 1930s with his founding publication in
1940.[3]
This reaction causes the expansion of the altered aggregate by the formation of a soluble and
viscous gel of sodium silicate (Na2SiO3 · n H2O, also noted Na2H2SiO4 · n H2O, or N-S-H (sodium
silicate hydrate), depending the adopted convention). This hygroscopic gel swells and increases
in volume when absorbing water: it exerts an expansive pressure inside the siliceous aggregate,
causing spalling and loss of strength of the concrete, finally leading to its failure.
ASR can cause serious cracking in concrete, resulting in critical structural problems that can
even force the demolition of a particular structure.[4][5]

Contents
[hide]

 1Chemistry
o 1.1Catalysis of ASR by NaOH or KOH
o 1.2Analogy with the soda lime carbonation
 2Mechanism of concrete deterioration
 3Structural effects of ASR
 4Mitigation
 5Treatment
 6ASR test
 7Known affected structures
o 7.1Australia
o 7.2Belgium
o 7.3Canada
o 7.4Germany
o 7.5New Zealand
o 7.6United Kingdom
o 7.7United States
 8See also
 9External links
 10References

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)4 or 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 fracture. It is the hydro-
mechanical expansion of the damaged siliceous aggregate surrounded by
calcium-rich hardened cement paste which is responsible for 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).
(CO2 trapping by soluble
(1) CO2 + 2 NaOH → Na2CO3 + H2O
NaOH)
Na2CO3 + CaCO3 + 2
(2) → (regeneration of NaOH)
Ca(OH)2 NaOH
sum
CO2 + Ca(OH)2 → CaCO3 + H2O (global reaction)
(1+2)
In the presence of water or simply ambient moisture, the strong bases, NaOH or
KOH, readily dissolve in their hydration
water (hygroscopic substances, deliquescence phenomenon) 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 anesthesia systems.

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]

Structural effects of ASR[edit]

The cracking caused by ASR can have several negative impacts on concrete,
including:[7]

1. Expansion: The swelling nature of ASR gel increases the chance of

expansion in concrete elements.
2. Compressive Strength: The effect of ASR on compressive strength can
be minor for low expansion levels, to relatively higher degrees at larger
expansion. (Swamy R.N 1986) points out that the compressive strength
is not very accurate parameter to study the severity of ASR; however,
the test is done because of its simplicity.
3. Tensile Strength / Flexural Capacity: Researches show that ASR
cracking can significantly reduce the tensile strength of concrete;
therefore reducing the flexural capacity of beams. Some research on
bridge structures indicate about 85% loss of capacity as a result of ASR.
4. Modulus of Elasticity/UPV: The effect of ASR on elastic properties of
concrete and ultrasound pulse velocity (UPV) is very similar to tensile
capacity. The modulus of elasticity is shown to be more sensitive to
ASR than pulse velocity.
5. Fatigue: ASR reduces the load bearing capacity and the fatigue life of
concrete (Ahmed T 2000).
6. Shear: ASR enhances the shear capacity of reinforced concrete with
and without shear reinforcement (Ahmed T 2000).

Mitigation[edit]
ASR can be mitigated in new concrete by several complementary approaches:

1. Limit the alkali metal content of the cement. Many standards impose
limits on the "Equivalent Na2O" content of cement.
2. Limit the reactive silica content of the aggregate. Certain volcanic rocks
are particularly susceptible to ASR because they contain volcanic glass
(obsidian) and should not be used as aggregate. The use of calcium
carbonate aggregates is sometimes envisaged as an ultimate solution
to avoid any problem. However, while it may be considered as a
necessary condition, it is not a sufficient one. In
principle, limestone (CaCO3) is not expected to contain a high level of
silica, but it actually depends on its purity. Indeed, some siliceous
limestones (a.o., Kieselkalk found in Switzerland)[8] may be cemented by
amorphous or poorly crystalline silica and can be very sensitive to the
ASR reaction, as also observed with some Tournaisian siliceous
limestones exploited in quarries in the area of Tournai in Belgium.[9] In
Canada, the Spratt siliceous limestone is also particularly well known in
studies dealing with ASR and is commonly used as the Canadian ASR
reference aggregate. So, the use of limestone as aggregate is not a
guarantee against ASR in itself.
3. Add very fine siliceous materials to neutralize the excessive alkalinity of
cement with silicic acid by deliberately provoking a controlled pozzolanic
 reaction at the early stage of the cement setting. Convenient pozzolanic
materials to add to the mix may be, e.g., pozzolan, silica fume, fly ash,
or metakaolin.[10] These react preferentially with the cement alkalis
without formation of an expansive pressure, because siliceous minerals
in fine particles convert to alkali silicate and then to calcium silicate
without formation of semipermeable reaction rims.
4. Another method to reduce the ASR is to limit the external alkalis that
come in contact with the system.
In other words, as it is sometimes possible to fight fire with fire, it is also feasible
to combat the ASR reaction by itself. A prompt reaction initiated at the early
stage of concrete hardening on very fine silica particles will help to suppress a
slow and delayed reaction with larger siliceous aggregates on the long term.
Following the same principle, the fabrication of low-pH cement also implies the
addition of finely divided pozzolanic materials rich in silicic acid to the concrete
mix to decrease its alkalinity. Beside initially lowering the pH value of the
concrete pore water, the main working mechanism of silica fume addition is to
consume portlandite (the reservoir of hydroxyde (OH–) in the solid phase) and to
decrease the porosity of the hardened cement paste by the formation of calcium
silicate hydrates (C-S-H). However, silica fume has to be very finely dispersed in
the concrete mix, because agglomerated flakes of compacted silica fume can
themselves also induce ASR if the dispersion process is insufficient. This can be
the case in laboratory studies made on cement pastes alone in the absence of
aggregates. However, most often, in large concrete batches, silica fume is
sufficiently dispersed during mixing operations of fresh concrete by the presence
of coarse and fine aggregates.
As part of a study conducted by the Federal Highway Administration, a variety of
methods have been applied to field structures suffering from ASR-affected
expansion and cracking. Some methods, such as the application of silanes,
have shown significant promise, especially when applied to elements such as
small columns and highway barriers, whereas other methods, such as the
topical application of lithiumcompounds, have shown little or no promise in
reducing ASR-induced expansion and cracking.[11]

Treatment[edit]
There are no treatments in general in affected structures. Repair in damaged
sections is possible, but the reaction will continue. In some cases, drying of the
structure followed by the installation of a watertightmembrane can stop the
evolution of the reaction.
Massive structures such as dams pose particular problems: they cannot be
easily replaced, and the swelling can block spillway gates or turbine operations.
Cutting slots across the structure can relieve some pressure, and help restore
geometry and function.

ASR test[edit]
Some ASTM Tests that screen aggregate for the potential of ASR include:

 ASTM C227: “Test Method for Potential Alkali Reactivity of Cement-

Aggregate Combinations (Mortar-Bar Method)”
 ASTM C289: "Standard Test Method for Potential Alkali-Silica Reactivity of
Aggregates (Chemical Method)"
 ASTM C295: “Guide for Petrographic Examination of Aggregate for
Concrete”
 ASTM C1260: “Test Method for Potential Reactivity of Aggregates (Mortar-
Bar-Test)”. It is a rapid test of aggregates: immersion of mortar bars in
NaOH 1 M at 80 °C for 14 days used to quickly identify highly reactive
aggregates or quasi non-reactive aggregates.
 ASTM C1293: “Test Method for Concrete Aggregates by Determination of
Length Change of Concrete Due to Alkali-Silica Reaction”. It is a long-term
confirmation test (1 or 2 years) at 38 °C in a water-saturated moist
atmosphere (inside a thermostated oven) with concrete prisms containing
the aggregates to be characterised mixed with a high-alkali cement specially
selected to induce ASR. The concrete prisms are not directly immersed in
an alkaline solution, but wrapped with moist tissues and tightly packed
inside a water-tight plastic foils.
 ASTM C1567: "Standard Test Method for Determining the Potential Alkali-
Silica Reactivity of Combinations of Cementitious Materials and Aggregate
(Accelerated Mortar-Bar Method)"
 The Oberholster method on which the ASTM C1260 test is based.
 The Dungan method with superimposed additional thermal cycles.
 The concrete microbar test was proposed by Grattan-Bellew et al. (2003) as
a universal accelerated test for alkali-aggregate reaction.[12]