Sulphate attack

Sulphate attack occurs as a result of the ingress of dissolved sulphate ions into concrete, which
subsequently undergo reactions with the hardened cement. Depending on the exposure
conditions, a number of different reactions are possible, whose impact on concrete properties
results either from expansion and cracking or loss in strength and integrity. These different
effects will be examined subsequently. However, it is first useful to examine where sulphates
arise in the environment.
Sulphate in the Environment
Sulphates can arise from two main sources in the environment seawater and soil and
groundwater. These sources are discussed below.
1) Sea water
Seawater contains relatively large concentrations of sulphate ions between 2500 and 3000
milligrammes per litre (mg/L), depending on the salinity of the water. The anion is associated
with sodium and magnesium cations and, to a lesser extent, potassium and calcium ions. Using
typical proportions of association, MgSO4 can be estimated to be present at concentrations
between 2400 and 2900 mg/L, with Na2SO4 present at concentrations between 4800 and 5800
mg/L. The high concentrations of magnesium sulphate mean that seawater can potentially be a
relatively aggressive sulphate environment.
2) Soil and Ground water
The extent to which sulphate in soil is available for ingress into concrete depends on the
solubility of the minerals present, as well as the extent to which groundwater is present and its
mobility. Soil can potentially contain a number of sulphate minerals, although some of these are
of low solubility. Common sulphate minerals are shown in Table, which shows that the most
soluble are sodium and magnesium sulphates. Sulphide minerals such as pyrite, marcasite and
pyrrhotite may also be present. Most of these sulphide minerals are of very low solubility. In
undisturbed soils rich in sulphide minerals, sulphate will only be present in significant quantities
in the first few metres of soil that has undergone long-term weathering processes that have led to
the gradual oxidation of sulphides.
Moreover, the first metre of soil will typically contain relatively low levels of sulphate
resulting from leaching to lower levels by infiltrating rainwater.
Disruption of soil during construction can potentially bring sulphide minerals in contact with air,
which allows the minerals to be oxidised to sulphate minerals at a relatively high rate. In highpH conditions, such as those produced in close proximity to hydrated Portland cement, this
process can be accelerated. Sulphur-oxidising bacteria, which may be present in soil, are also
capable of converting sulphide minerals into sulphates. In both cases, sulphide is oxidised to
sulphuric acid, which proceeds to react with other cations in the soil to form sulphate
compounds.
Peaty soils are also rich in sulphur, although much of this is present as organic
compounds rather than as inorganic minerals. However, this too can be oxidised to sulphate as a
result of soil disruption.
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S.Praveenkumar/Assistant Professor/Department of Civil Engineering/PSGCT

Human activities may also introduce sulphur onto sites. Previous industrial operations
particularly those involving the handling and processing of fossil fuels may contaminate soil
with sulphates and sulphides. Activities of this type include coal mining, gas and coke processing
plants and iron and steel manufacture. Additionally, activities such as fertilizer manufacture and
metal finishing may also introduce sulphates onto a site.
In some cases, sulphate-bearing by-products from industrial activities may be introduced
onto sites as granular fill. These include blast-furnace slag, colliery spoil, furnace bottom ash
from coal-fired power generation and incinerator bottom ash from the combustion of municipal
waste. Demolition rubble can also potentially contain reasonably large quantities of soluble
sulphate.

Sulphate attack
The presence of soluble sulphates (Principally those of sodium, calcium and magnesium) is
common in areas of mining operations, chemical and paper milling industries. Sodium and
calcium are most common sulphates in soils, water and industrial processes. Magnesium
sulphates are less common, but more destructive. Soils or waters containing these sulphates are
often called alkali soils or waters.
All sulphates are potentially harmful to concrete. They react chemically with cement
pastes hydrated lime and hydrated calcium aluminates. As a result of this reaction, solid
products entering the reaction are formed.
The formation of gypsum and ettringite expands, pressurizes and disrupts the paste. As a
result, surface scaling and disintegration set in, followed by mass deterioration.
Mechanism
The most commonly encountered form of sulphate attack occurs in parallel with the
formation of ettringite (3CaOAl2O3 (CaSO4)332H2O) as a reaction product.
This type of attack occurs when the cations associated with the sulphate ions are sodium,
potassium or calcium. Ettringite is a reaction product of Portland cement hydration and plays
an important role during the early setting and hardening of cement.
However, when formed within relatively mature concrete in large enough quantities, the
effect can be problematic.

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S.Praveenkumar/Assistant Professor/Department of Civil Engineering/PSGCT

 For ettringite to be formed by sulphate ions entering hardened concrete, the sulphate needs to
come into contact with a source of aluminum and calcium.
In a mature cement paste, aluminum is present as ettringite, Al2O3Fe2O3mono (AFm)
hydration products or is substituted within the calcium silicate hydrate (CSH) gel.
Aluminum from AFm phases is usually more soluble than that from CSH gel, and so it is
normally these phases that are involved in ettringite formation.
Normally, the AFm phase present will be monosulphate (3CaOAl2O3CaSO412H2O),
although mix constituents and environmental conditions may produce AFm phases including
Friedels salt (3CaOAl2O3CaCl210H2O),
Monocarbonate (3CaOAl2O3CaCO311H2O) and
Hemicarbonate (3CaOAl2O31/2CaCO31/2CaO.12H2O).
The reaction with monosulphate is as follows:

The additional calcium required for this reaction is obtained from different sources,
depending on the cation associated with sulphate.
Where sulphate is present as CaSO4, the associated ion provides all of the calcium required
for the reaction.
However, where sodium or potassium sulphate is involved, calcium comes either from the
hydration products portlandite (Ca (OH) 2) or CSH gel.
Where calcium is obtained from CSH gel, the Ca/Si ratio of the gel declines, and the gel is
said to have become decalcified. When no further AFm phases remain, the sulphate ions
combine with calcium ions to form gypsum (CaSO42H2O).
It is often stated that the expansion of concrete undergoing this type of sulphate attack is the
result of the solid volume of ettringite being significantly greater than that of solid reactants.
However, this is true of other cement hydration products, yet their precipitation has little
impact on paste volume.
It has been proposed that the expansion is the result of the decalcification of CSH gel, which
leads to greater swelling of the gel as a result of water imbibitions.
Regardless of whether this is the case; decalcification will lead to loss in strength.
Methods of controlling sulphate attack
Sulphate resistance of concrete can be improved by reduction in water cement ratio and
an adequate cement factor, with a low tricalcium aluminate and with proper air entrainment.
With proper proportioning, silica fume, fly ash and GGBS generally improve the resistance of
concrete to sulphate attack, primarily by reducing the amount of reactive elements (such as
calcium) needed for expansive sulphate reactions. Generally the methods for controlling sulphate
attack are
a) Use of sulphate resisting cement
b) Quality concrete
c) Use of air-entrainment
d) Use of pozzolana
e) High pressure steam curing
f) Use of high alumina cement
Complied by
S.Praveenkumar/Assistant Professor/Department of Civil Engineering/PSGCT

Complied by
S.Praveenkumar/Assistant Professor/Department of Civil Engineering/PSGCT

a) Use of sulphate resisting cement

The most efficient method of resisting the sulphate attack is to use cement with low C3A content.
In general, it has been found that a C3A content of 7% gives a rough division between cements of
good and poor performance in sulphate waters.
b) Quality concrete
As well designed, placed and compacted concrete which is dense and impermeable exhibits a
higher resistance to sulphate attack. Similarly, a concrete with low water/cement ratio also
demonstrates a higher resistance.
c) Use of air-entrainment
Use of air-entrainment to the extent of about 6% has beneficial effect on the sulphate resisting
qualities of concrete. The beneficial effect is possibly due to reduction of segregation,
improvement in workability, reduction in bleeding and in general better impermeability of
concrete.
d) Use of Pozzolana
Incorporation of or replacing a part of cement by a pozzolanic material reduces the sulphate
attack. Admixing of pozzolana converts the leachable calcium hydroxide into insoluble nonleachable cementitious product. This pozzolanic action is responsible for impermeability of
concrete. Secondly, the removal of calcium hydroxide reduces the susceptibility of concrete to
attack by magnesium sulphate.
e) High pressure steam curing
High pressure steam curing improves the resistance of concrete to sulphate attack. This
improvement is due to the change of C3AH6 into a less reactive phase and also to the removal or
reduction of calcium hydroxide by the reaction of silica which is invariably mixed when a high
pressure steam curing method is adopted.
f) Use of High Alumina cement
The cause of great resistance shown by high alumina cement to the action of sulphate is still not
fully understood. However, it is attributed in part to the absence of any free calcium hydroxide in
the set cement, in contrast to Portland cement. High alumina cement contains approximately
40% alumina, a compound very susceptible to sulphate attack, when in normal Portland cement.
But this percentage of alumina cement behaves in a different way. The primary cause of
resistance is attributed to formation of protective films which inhibit the penetration or diffusion
of sulphate ions into interior it. It should be remembered that high alumina cement may not be
show higher resistance to sulphate attack at higher temperature.

Complied by
S.Praveenkumar/Assistant Professor/Department of Civil Engineering/PSGCT