Alkali-silica reaction (ASR)

Concrete can be damaged by a chemical reaction between the active silica constituents of the
aggregate and the alkalis in the cement; this process is known as alkali silica reaction. In the context
of ASR, the alkalis are the metal alkalis sodium and potassium. However, the alkali-silica reaction is a
reaction between the hydroxyl ions in the pore water of a concrete and certain forms of silica which
occasionally occur in significant quantities in the aggregate. It is not primarily a reaction between
sodium and potassium ions and reactive silica. The hydration of a Portland cement results in a pore
solution containing calcium, sodium and potassium hydroxides. Most of the calcium hydroxide
produced during hydration is present as a crystalline hydroxide but most of the metal hydroxides are
present in the pore solution.
The reactive forms of silica are opal (amorphous), chalcedony (cryptocrystalline fibrous), and
tridymite (crystalline). These materials accour in several types of rocks: opaline or chalcedonic
cherts, siliceous limestones, rhyolites and rhyolitic tuffs, dacite and dacite tuffs, andesite and
andesite tiffs, and phyllites. Since lightweight aggregates are often composed of predominantly
amorphous silicates, they appear to have the potential for being reactive with alkali in cement.
However, there is no evidence of damage of lightweight aggregate concrete caused by alkaliaggregate reaction. Aggregates containing reactive silica are found mostly in the western part of the
US, and to a much smaller extent in the Midlands and South-West of the UK. They are found also in
numerous other countries.
DELETERIOUSLY REACTIVE ROCKS, MINERALS AND SYNTHETIC SUBSTANCES
Reactive substance
Opal
Chalcedony

Chemical composition
SiO2 nH2O
SiO2

Certain forms of quartz

SiO2

Cristobalite
Tridymite
Rhyolitic, dacitic, latitic,
or andesitic glass or
cryptocrystalline
devitrification products
Synthetic siliceous
glasses

SiO2
SiO2
Siliceous, with lesser
proportions of A12O3,
Fe2O3, alkaline earths,
and alkalies
Siliceous, with lesser
proportions of
alkalies, alumina,
and/or other
substances

Physical character
Amorphous
Microcrystalline to
cryptocrystalline;
commonly fibrous
a) Microcrystalline to
cryptocrystalline
b) Crystalline, but
intensely fractured,
strained, and/or
inclusion-filled
Crystalline
Crystalline
Glass or cryptocrystalline
materials as the matrix
of volcanic rocks or
fragments in tuffs
Glass

The most important deleteriously alkali-reactive rocks (that is, rocks containing excessive amounts of
one or more of the substances listed above) are as follows:
Opaline cherts
Chalcedonic cherts
Quartzose cherts
Siliceous limestones
Siliceous dolomites
Rhyolites and tuffs
Dacites and tuffs

Andesites and tuffs

Siliceous shales
Phyllites
Opaline concretions
Fractured, strained and inclusionfilled quartz and quartzites

Note : A rock may be classified as for example, a siliceous limestone and be

innocuous it its siliceous constituents are other than those indicated above.
(b)
Figure 5-14 Alkali-reactive rocks in Portland cement concrete. [(a), Based on R.F. Blanks and H.L.
Kennedy, The Technology of Cement and Concrete. Vol. 1, John Wiley & Sons, Inc., New York, 1955;
(b), from ACI Committee 201, J. ACI. Proc., Vol. 74. P. 598, 1977)
Combination of high-alkali Portland cement (>0.6 percent equivalent Na2O) and certain siliceous
aggregates used for making concrete for several U.S dams showed undesirably large expansions in
mortar prisms [part (a)]. The same aggregates showed only small expansions when a low-alkali
cement was used in the test. A comprehensive list of alkali-reactive aggregates is given in part (b)

The reaction starts with the attack of the siliceous minerals in the aggregate by the alkaline
hydroxides derived from the alkalis (Na2O and K2O) in the cement.

The alkali-silicate gel formed attracts water by absorption or by osmosis and thus tends to increase in
volume. Since the gel is confined by the surrounding cement paste, internal pressures result and
eventually lead to expansion, cracking and disruption of the cement paste, pop-outs and spalling, and
to map cracking of the concrete.

Expansion of the cement paste appears to be due to the hydraulic pressure generated by osmosis,
but expansion can also be caused by the swelling pressure of the still solid products of the alkali-silica
reaction. For this reason, it is believed that it is the swelling of the hard aggregate particles that is
most harmful to concrete. The speed with which the reaction occurs is controlled by the size of the
siliceous particles: fine particles (20 to 30 m) lead to expansion within four to eight weeks while
larger ones do so only after some years. It is generally the very late occurrence of damage due to the
alkali-aggregate reaction, often after more than five years, that is a source of worry and uncertainly.

Stage 1 gel grows inducing internal stresses, no micro-cracking ; Stage 2 induced stresses large
enough to cause micro-cracking in vicinity of reacting particles, negligible expansion; Stage 3 gel
migrates into micro-cracks, buildup of internal stresses; Stage 4 internal stresses large to cause
micro-cracking and large expansion

Other factors influencing the progress of the alkali-aggregate reaction are the porosity of the
aggregate, the quantity of the alkalis in the cement, the availability of water in the paste and the
permeability of the cement paste. The reaction takes place mainly in the exterior of the concrete
under permanently wet conditions, or when there is alternating wetting and drying, and at higher
temperatures (in the range: 10 to 38 C (50 F to 100 F)); consequently, avoidance of these
environments is recommended.
Although it is known that certain types of aggregate tend to be reactive, there is no simple way of
determining whether a given aggregate will cause excessive expansion due to reaction with the
alkalis in cement. For potentially safe aggregates, service records have generally to be relied upon
but as little as 0.5 per cent of vulnerable aggregate can cause damage.
In the US, a petrographic examination of aggregates is prescribed by ASTM C 295-79, which indicates
the amount of reactive minerals but these are not easily recognized especially when there is no
previous experience of the aggregate. There exists also a chemical method (ASTM C 289-81) but
again this method is not reliable. Probably the most suitable test is the mortar-bar test (ASTM C 22781). Here, the suspected aggregate, crushed if necessary and made up to a prescribed grading, is
used to make special sand-cement mortar bars, using a cement with an equivalent alkali content of
not less than 0.6 per cent. The bars are stored aver water at 38 C (100 F), at which temperature the
expansion is more rapid and usually higher than at higher or lower temperatures. The reaction is
also accelerated by the use of a fairly high water/cement ratio. The aggregate under test is
considered harmful if it expands more than 0.05 per cent after 3 months or more than 0.1 per cent
after 6 months. The ASTM mortar-bar test has not been found to be suitable for UK aggregate. Here,
tests on concrete specimens are generally thought to be more appropriate but such tests have yet to
be devised.

To minimize the risk of alkali-silica reaction the following precautions are recommended in the UK:
(a) Prevent contact between the concrete and external source of moisture.
(b) Use Portland cements with an alkali content of not more than 0.6 per cent expressed as
Na2O. (This is the sum of the actual Na2O content plus 0.658 times the K2O content of
the cement)
(c) Use a blend of ordinary Portland (Type I) cement and ground granulated blast-furnace
slag, with a minimum of 50 per cent of slag.

(d) Use a blend of ordinary Portland (Type I) cement and PFA with a minimum of 25 per cent
of PFA (fly ash), provided that the alkali content of the concrete supplied by the Portland
cement component is less than 3.0 kg/m3 (5.0 lb/yb3). The alkali content of concrete is
calculated by multiplying the alkali content of Portland cement (expressed as a fraction)
by the maximum expected Portland cement content.
(e) Limit the alkali content of the concrete to 3.0 kg/m3 (5.0 lb/yb3) which is now the alkali
content of the composite cement (expressed as a fraction times the maximum expected
content of the cementitious material)
(f) Use a combination of aggregated which is judged to be potentially safe.

We should note that neither slag nor PFA is assumed to contribute reactive alkalis to the concrete,
although those materials have fairly high levels of alkalis. However, most of these alkalis are
probably contained in the glassy structures of the slag or PFA and take no part in the reaction with
aggregate. Moreover, the silica in PFA, paradoxically, attenuates the harmful effects of the alkalisilica reaction. The reaction still takes place, but the finely-divided siliceous material in PFA forms,
preferentially, an innocuous product. In other words, there is a pessimum content of reactive silica
in the concrete above which little damage occurs.
In the US, ACI 201.2R-77 (reaffirmed 1982) recommends the use of a low alkali cement (not more
than 0.6 per cent) and the use of a suitable pozzolanic material, as prescribed by ASTM C618-84. If
potentially deleterious, cement-aggregate combinations cannot be avoided, the use of a pozzolan
and of at least 30 per cent (by mass) of limestone coarse aggregate is recommended. It is important,
however, that the resulting concrete should not exhibit an increase in shrinkage or a reduced
resistance to frost damage (with air entertainment, of course). To put it more generally, it is vital to
guard against introducing new undesirable features of concrete while curing other ills.