Sulfate Attack

Sulfate attack is the reaction between sulfate ions in the pore solution of concrete
and constituents in the concrete that result in formation of new reaction products
with a relatively large molar volume.

From: Non-Destructive Evaluation of Reinforced Concrete Structures: Deterioration

Processes and Standard Test Methods, 2010

Related terms:

Fly Ash, Corrosion, Binders, Compressive Strength, Cement Paste, Ettringite, Port-
land Cement, Sulfate Solution, Sulphate Resistance

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Learn more about Sulfate Attack

Deterioration processes in reinforced

concrete: an overview
D. Breysse, in Non-Destructive Evaluation of Reinforced Concrete Structures: Dete-
rioration Processes and Standard Test Methods, 2010

Fundamental processes: causes and mechanisms

Sulfate attack is another possible deterioration mechanism of concrete. It can have
endogenous origin (developing without any contribution from the environment) or
exogenous origins (such as sulfates contained in the soils or in liquids) (Germain,
2008; Neville, 2004). In both cases, the consequence is some volume expansion
owing to the delayed formation of ettringite, which is an expansive component.
The internal sulfate attack is characterized by a delayed mobilization of cement
sulfates, and it leads to the generalized deterioration of the concrete. The main
cause is a high elevation of the temperature, which can be encountered in the case
of massive structures (see Section 3.2.2) or during precasting while using steam
curing. The word ‘delayed’ indicates that ettringite could not form (as is the usual
process) during the cement hydration, because of an overly elevated temperature
(ettringite is destroyed over 70 °C). It then appears several weeks, months or years
after the casting. Damage to the concrete occurs when the ettringite crystals exert an
expansive force within the concrete as they grow. The material volume expansions,
similarly to what happens with AAR, creates a crack network on the structure surface
(Fig. 3.7) (Carles-Gibergues and Hornain, 2008).

3.7. Cracking pattern in a bridge suffering from internal sulfatic attack (from Ger-
main, 2008).

The first case of internal sulfate attack was identified in 1987 in Finland, in precast
concrete specimens for railway tracks, although external sulfate attack had been
recognized since 1887 with problems owing to interaction with gypsum on walls in
Paris. External sulfate attack is a chemical breakdown mechanism where sulfate ions
from an external source (underground water, sea water, some earthworks) attack
components of the cement paste. Such attack can occur when concrete is in contact
with sulfate-containing water, e.g. seawater, swamp water, ground water or sewage
water. The often massive formation of gypsum and ettringite formed during the
external sulfate attack may cause concrete to crack and scale. For external sulfate
attack, the reaction propagates from the surface towards the concrete core. A specific
context of sulfate attack is that of the sewer system where biological processes and
unsufficient air ventilation can provoke the accumulation of hydrogen sulfide (H2S)
which, after transformation by sulfo bacteria in sulfuric acid (H2SO4), attacks the
cement paste, leachates the portlandite and also forms secondary ettringite.

The apparent pathology of sulfate attack is similar to that of AAR, thus preventing
the two phenomena being distinguished without a microstructural analysis.

> Read full chapter

Types and causes of cracking in con-
crete structures
C.J. Larosche, in Failure, Distress and Repair of Concrete Structures, 2009

Sulfate reaction
Sulfate attack can affect concrete through either internal or external reactions.
General sulfate-related distress observed on the surface of concrete is referred to as
external sulfate attack (or simply sulfate attack). External sulfate attack occurs when
soil and groundwater contain sufficient sulfate levels, in the forms of sodium,
potassium, magnesium, or calcium sulfate, which react with the cementitious paste
of the concrete. Generally, deterioration starts at the contact zone between the
concrete and the sulfate-containing environment, forming a propagating front.
While concrete ahead of this front is essentially normal, concrete behind this front
is completely changed in composition and texture, with its integrity significantly
lost. Initially, sulfate reacts with the monosulfur aluminate phase of the paste from
the cement hydration, forming ettringite, C3A · 3CS · H32. These reactions are
highly expansive, and will generate stresses exceeding the tensile strength of the
concrete, resulting in cracking and disintegration of the concrete. In later stages,
most of the cement paste may be replaced by ettringite and gypsum. The extent
of sulfate attack, however, often depends on the quality of the concrete and the
type of sulfate. More porous concrete (higher w/cm) may be more readily attacked
than low-permeability concrete. Magnesium sulfate is generally more aggressive
than other forms of sulfate because magnesium ions also participate in the reaction,
replacing calcium and forming brucite (magnesium hydroxide). Calcium sulfate is
usually the least reactive. An illustration of a more aggressive sulfate attack is shown
in Fig. 3.7.
3.7. Sulfate attack at the base of a conventionally reinforced concrete column

Sulfate attack can be progressive: as long as sulfate ions can penetrate the con-
crete surface, further reaction may occur throughout the concrete interior. This
mechanism has been understood by engineers for many years and, as a result,
cements of Type II and Type V containing less than 8% and 5% C3A, respectively are
specified to mitigate sulfate attack. Limitations on concrete w/cm are often required,
with the intent of lowering surface absorption of sulfate ions into the concrete.
In addition, supplementation with silica fume, fly ash, and ground slag has been
proven to provide resistance to sulfate attack, provided that the C3A content of the
cementitious material system is limited, and the impermeability of the concrete
matrix is preserved.

Sulfates in the soil or groundwater should be measured if sulfate attack is suspected.

Sulfate ions are commonly measured in parts per million (ppm) and the scale of
severity, according to the ACI 318 Building Code for Concrete (ACI, 2008, Table 4.2.1)
is:

• Negligible – When sulfate content is less than 150 ppm (mg/l) in water, no

restriction on cement type is necessary.
• Moderate – When sulfate content is between 150 and 1500 ppm in water, Type
II cement with a pozzolan additive should be used.
• Severe – When the sulfate content is between 1500 and 10 000 ppm in water,
Type V cement should be used, along with a w/cm ratio below 0.45.
• Very severe – When the sulfate content exceeds 10 000 ppm in water, Type V
cement should be used with a pozzolan and a w/cm of below 0.45. In addition,
the ACI Building Code recommends a minimum f c of 29 MPa (4250 psi)
(Mehta and Monteiro, 2006).
> Read full chapter

Durability of concrete structures

Peter A. Claisse, in Civil Engineering Materials, 2016

25.4 Sulphate attack

Sulphate attack occurs in concrete when sulphates from the surrounding environ-
ment react with the calcium hydroxide, and calcium aluminate hydrate in hardened
cement paste. The products of the reactions – gypsum and calcium sulphoaluminate
– have considerably greater volume than the compounds that they replace, so the
reactions lead to expansion and disruption of the concrete. Common sources of
sulphate for attack on concrete are:

• Groundwater.

• Sulphate-rich soils.

• Seawater.

• Demolition hardcore that contains gypsum plaster.

The usual method of prevention of sulphate attack is to use sulphate resisting ce-
ment, or additions/replacements to the cement (particularly, GGBS). If the structure
has not been adequately protected in this way, any repair must effectively prevent
further penetration of sulphates.

Thaumasite formation is a different type of sulphate attack. This has caused prob-
lems in a number of structures, even when sulphate resisting cement has been used,
because it does not need a high alumina content to progress. It has been observed
in concrete footings, and depends on ground conditions. The process causes the
concrete to disintegrate and, even before this happens, it reduces chloride binding.

> Read full chapter

Concrete Aggregates
Ian Sims, Bev Brown, in Lea's Chemistry of Cement and Concrete (Fourth Edition),
1998

Sulfate actions
Sulfate attack is one of the most damaging causes of concrete deterioration, causing
either softening and decay of the concrete matrix (the ‘acid’ type of sulfate attack) or
expansive cracking and other disruption associated with the formation of ettringite
(calcium sulfoaluminate hydrate) and other reaction products within the hardened
concrete. Good summaries of sulfate attack are given by Figg308 and Eglinton;309
more extensive treatments may be found in Swenson310 and an American Concrete
Institute publication.311

These reactions largely involve the cement paste, rather than the aggregates, and are
not further considered in this chapter. However, in some unusual circumstances,
the sulfate action may derive from a constituent of the aggregate, or the aggregate
itself might be vulnerable to attack. Aggregates which are contaminated by sulfate
minerals can cause ‘internal’ sulfate attack, and many such materials have given rise
to problems in the Middle East.16,81,312 Particles of gypsum present in natural sands
from Bahrain, for example, were observed by Hussen312 to react within concrete,
forming calcium hydroxide (portlandite) and ettringite. Samarai,313 in experiments
in Iraq using powdered gypsum in mortar bars, produced unacceptably high expan-
sions with Portland cement concrete mixtures containing total sulfate contents in
excess of 5 per cent by weight of cement.

French and Crammond314 identified the cause of expansion of concrete and mortar
made with serpentinite wadi aggregates from the United Arab Emirates as being
internal sulfate attack involving contamination of the aggregate by up to 5 per cent
coarsely crystalline gypsum (Figure 16.31), and later work by Crammond84 found
that up to 2.5 per cent coarsely crystalline gypsum (or about 6 per cent total sulfate
by weight of cement) could be tolerated for Portland cement concrete (Figure 16.32).
Fig. 16.31. Scanning electron photomicrograph of internal sulfate attack in concrete
from the Arabian Gulf area (from Ref. 314). The view shows the interface between a
gypsum particle (top, out of view) and the cement paste (bottom); portlandite crystals
have developed (top half ) with associated acicular crystals of ettringite.

Fig. 16.32. Effect of coarsely crystalline gypsum in aggregate on the expansion of

mortar made using ordinary Portland cement containing 14% tricalcium aluminate
(C3A). Appreciable expansion overall with 5% gypsum, especially at the lower tem-
perature of 20°C.
(Building Research Establishment: Crown copyright 1990.)

Copyright © 1990

In rare cases, pyrite (iron disulfide) in aggregate can decompose in concrete in a

complicated series of reactions with cement to form gypsum, ettringite and other
compounds with accompanying expansion.315 Other aggregates may themselves be
vulnerable to sulfate attack: Braga Reis,316 for example, has described expansive et-
tringite formation as the result of reactions between sulfates and kaolinised feldspar
in a weathered granite aggregate.

In a small number of documented cases worldwide,317–320 a particular form of sulfate

attack has been reported where concrete had been designed to resist sulfates. In
these limited cases a different reaction product, thaumasite (CaSiO3·CaCO3·CaSO-
4·15H2O) had been formed instead of the gypsum (CaSO4·2H2O) and ettringite

(3CaO·Al2O3·3CaSO4·31H2O) associated with normal sulfate attack. Laboratory

studies have shown that in certain circumstances in the presence of carbonate ions
the silicate hydrates can also be attacked and thaumasite is the predominant reaction
product formed.

The reaction appears to require consistently wet and cold conditions, but this and
any other contributing factors remain to be defined. In its worst case, thaumasite
formation can cause concrete to decay into a mush-like form losing its strength. It
occurs as needle-like crystals, similar in appearance to ettringite. Analytical methods
to determine sulfate contents of concrete are unable to distinguish between the two
different forms of attack, ettringite and thaumasite. Differentiation between these
two forms requires microscopical, X-ray diffraction or spectroscopic methods.

Crammond and Halliwell320 highlight the role of finely divided carbonate filler in
promoting the thaumasite type of sulfate action, indicating that aggregate type
can sometimes have an influence over the occurrence of that form of damage to
concrete.

> Read full chapter

Microscopic examination of deteriorat-

ed concrete
T.G. Nijland, J.A. Larbi, in Non-Destructive Evaluation of Reinforced Concrete Struc-
tures: Deterioration Processes and Standard Test Methods, 2010

Sulfate attack
Sulfate attack is the reaction between sulfate ions in the pore solution of concrete
and constituents in the concrete that result in formation of new reaction products
with a relatively large molar volume. If sufficient new phases are formed, stresses
can be induced in the concrete to such an extent that the concrete can undergo
cracking. The sulfate ions may either come from the concrete itself, that is, when the
sulfate content of the cement is excessively high or from external sources, when the
environment in which the concrete is placed is rich in sulfates.

There are two main forms of sulfate attack, each yielding an expansive product,
but with different compounds. The first and most common form of sulfate attack
involves reaction of sulfate ions with calcium hydroxide and tricalcium aluminate
hydrates in the cement paste leading to the formation of gypsum (CaSO4.2H2O)
and massive ettringite, (3CaO. Al2O3.3CaSO4.32H2O or Ca6Al2(OH)12(SO4)3.26H2O)
(Fig. 8.19). The reaction occurs at normal temperatures under relatively moist con-
ditions. Because the reaction begins with dissolution of calcium hydroxide from
the cement paste, a typical effect is an increase in the capillary porosity of the
cement paste. The second form of sulfate attack in concrete and other cement-based
composites leads to the formation of thaumasite (CaSiO3. CaCO3.CaSO4.15H2O or
Ca3Si(OH)6(CO3)(SO4).12H2O). It is similar to ettringite in its formation, however,
unlike ettringite in which tricalcium aluminate hydrates are involved, it is the calcium
silicate hydrates (the C-S-H, i.e. the main strength-giving component) within the
cement paste that are affected.

8.19. Microphotograph showing cracks and air voids filled with massive secondary
ettringite (plane polarized light, view 5.4 mm × 3.5 mm).

In general, structures affected by sulfate attack usually exhibit large deformations

caused by swelling leading to crack formation. At the construction level, the cracks
often form a polygonal network and very often contain colourless or white exu-
dations. In the laboratory, diagnosis of cores removed from structures affected by
sulfate attack begins with a visual inspection, using a hand lens or a stereomi-
croscope. The pattern of cracking, especially along the surface of the aggregate
particles can provide clues as to the cause of deterioration. For massive ettringite
or thaumasite formation, large, dense amounts of the ettringite or thaumasite
crystals are produced, causing some to precipitate as white exudations in most of
the voids at the surface of the cores and on the fractured or sawn surfaces. Small
amounts of these fillings can be scraped onto glass plates, dispersed in immersion
oil and examined with the aid of a transmitted light microscope. If deterioration
is caused by massive ettringite (Fig. 8.19) or thaumasite formation, dense almost
indistinguishable needle-like crystals, together with calcium carbonate crystals and
some fine sand or cement particles shall be detected. This preliminary diagnosis
gives an indication that the deterioration is most likely caused by massive ettringite
or thaumasite formation. Since the visual deterioration features of sulfate attack are
similar to other forms of attack, for instance, frost attack accompanied by leaching
of the cement paste, further diagnosis either by means of PFM or SEM–EDS is
required. Both techniques are equally suitable, but the PFM technique is more
suitable because larger thin sections with surface area of about 100 mm × 150 mm
can be investigated than in the case of SEM.

> Read full chapter

Durability of sustainable concrete ma-

terials
J. Bai, in Sustainability of Construction Materials, 2009

10.3.5 Sulfate attack

Sulfate attack is the most common form of chemical attack that the concrete
is subjected to. Sulfates are commonly found in soil, aggregates, sea water and
cements. The chemical consequences of sulfate attack on concrete components are
detailed below (Neville, 1995; Taylor, 1997; Hewlett, 1998; Skalny et al., 1998).

1 The formation of ettringite (calcium aluminate trisulfate), resulting in an

increase in solid volume, leading to expansion and cracking

2 The formation of gypsum (calcium sulfate dihydrate), leading to softening and

loss of concrete strength

Protection against sulfate attack can be achieved by using concrete with low [P NO
247] permeability, using cements with a low C3A content and blends of Portland
cement with pozzolans (thus reducing the available Ca(OH)2). Proper placement,
compaction, finishing and curing of concrete are essential to minimize the ingress
and movement of water, which is the carrier of the aggressive salts. Recommended
procedures for these operations are found in the Building Research Establishment
(BRE) Special Digest 1 (BRE, 2005). Krammart and Tangtermsirikul (2004) indicated
that the expansions of municipal solid waste ashes and calcium carbide waste
cements in sodium sulfate solution were lower than those of the control cement
when it was exposed to sulfate solution.

There are many factors affecting sulfate attack and also factors that mitigate the
attack. In general three approaches are adopted: (a) preventing sulfates from pene-
trating into concrete; (b) consuming as much Ca(OH)2 as possible in the hydrated
cement matrix through the use of pozzolans such as FA and GGBS; (c) using cement
with low C3A.

The first approach is very important and can be achieved by producing impermeable
concrete in order to stop or slow the penetration of sulfates into the concrete, thus
extending the service life of the concrete. For concrete structures in contact with
sulfate-bearing soils, protective linings such as the various proprietary self-adhesive
membranes, or protective coatings – such as bitumens, tars and epoxy resins – may
also be applied on exterior surfaces.

Pozzolans such as FA (Chindaprasirt et al., 2004; Zuquan et al., 2007), silica fume
(Roy et al., 2001; Ganjian and Pouya, 2005), metakaolin (Bai et al., 2002; Khatib and
Hibbert, 2005) and GGBS (Gollop and Taylor, 1996; Higgins, 2003;) can be employed
to effect improvement in the resistance of concrete to sulfate attack. The effect of
pozzolans is that the pozzolanic reactions consume Ca(OH)2 -, which is needed for
reaction with sulfates. In the meantime, blended cement concrete has less Ca(OH)2 -
due to the replacement of cement with pozzolans.

Finally, the formation of ettringite can be minimized by using sulfate-resisting

cement, which has a lower C3A content.

> Read full chapter

Concrete
Jeremy P. Ingham BSc (Hons), MSc, DipRMS, CEng, MInstNDT, EurGeol, CGeol,
CSci, FGS, FRGS, MIAQP, in Geomaterials Under the Microscope, 2013

SULFATE ATTACK FROM GROUNDWATER

Sulfate attack is a term used to describe a series of deleterious chemical reactions
between sulfate ions and the components of hardened concrete, principally the
cement matrix, caused by exposure of concrete to sulfates and moisture (Skalny et al.,
2002). The sulfates of greatest concern for the durability of concrete are salts found in
natural soils and groundwaters such as sulfates of sodium, potassium, magnesium,
and calcium. In addition, groundwater that has been contaminated with fertilizer or
industrial effluent may also contain ammonium sulfate. The mechanisms of sulfate
attack are complicated, involving a number of overlapping chemical reactions, which
are not yet fully understood. However, it is known that the extent of attack depends
on the amount of sulfate in solution and that the aggressiveness of the sulfate salts is
broadly related to their solubility. The solubility of sulfate salts running from most to
least is: ammonium, magnesium, sodium, potassium, and calcium. Calcium sulfate
(found in gypsum-bearing soils) attacks only the calcium aluminate phase of the
cement matrix to form ettringite (calcium sulfoaluminate) as follows.

Calcium aluminate hydrates + CaSO4.2H2O → 3CaO.Al2O3.3CaSO4.32H2O

The other sulfate salts (ammonium, magnesium, sodium, potassium) react with
calcium hydroxide (portlandite) in the concrete to form calcium sulfate (gypsum)
as shown below. This calcium sulfate may then interact with the calcium aluminate
phase to form ettringite, as in the reaction detailed above (St John et al., 1998).

(NH4)2SO4 + Ca(OH)2 + 2H2O → CaSO4.2H2O + 2NH3

MgSO4 + Ca(OH)2 + 2H2O → CaSO4.2H2O + Mg(OH)2

Na2SO4 + Ca(OH)2 + 2H2O → CaSO4.2H2O + 2NaOH

K2SO4 + Ca(OH)2 + 2H2O → CaSO4.2H2O + 2KOH

Magnesium sulfate also attacks the calcium silicate phases of the cement matrix
to form gypsum, brucite (magnesium hydroxide), and hydrated silica. Below a pH
of 10.6, it may also attack ettringite to form more gypsum, brucite, and hydrated
alumina (St John et al., 1998).

Sulfate attack from an external source of sulfates (such as groundwater) will exhibit
a zone of deterioration that works inwards from the surfaces exposed to the sul-
fates. Deterioration manifests itself, firstly, by causing cracking associated with the
expansive formation of ettringite and/or gypsum and, secondly, by the dissolution
and weakening of the cement matrix. Petrographically, the cracks and microcracks
will be observed in thin section along with secondary deposits of sulfate minerals
(usually ettringite or gypsum) filling cracks and air voids. Figure 203 shows concrete
from a pile cap of a flyover that exhibits evidence of sulfate attack consisting of a
network of microcracks and air voids filled with ettringite. Ettringite is identified
from its small, needle-like crystals, first-order grey interference colours, and its
colourless appearance in plane-polarized light. Fluorescent microscopy can be used
to highlight the cracks produced by deterioration and Figure 204 shows this for an
example of a pile from a building suffering from external sulfate attack.
203. Close view of concrete suffering from external sulfate attack, showing small air
voids and microcracks packed with acicular ettringite crystals (grey). The uncarbon-
ated cement matrix appears portlandite depleted (black); XPT, ×150, 1mm across.

204. Fluorescent microscopy of concrete suffering from external sulfate attack,

showing microcracks (yellow) running through the cement matrix and connecting
with ettringite-filled air voids; UV, ×150, 1mm across.

Guidance regarding the design of buried concrete elements that may be exposed
to sulfates of other aggressive ground conditions is given in BRE Special Digest 1
(Building Research Establishment, 2005).

> Read full chapter

Durability of sustainable construction

materials
J. Bai, in Sustainability of Construction Materials (Second Edition), 2016

16.3.5 Sulphate attack

Sulphate attack on concrete is the most common form of chemical attack. Sulphates
are commonly found in soil, aggregates, seawater, and cements. The chemical
consequences of sulphate attack on concrete components are (Hewlett, 2003; Hobbs
and Taylor, 2000; Tang et al., 2015):

● the formation of ettringite (calcium aluminate trisulphate), resulting in an

increase in solid volume, leading to expansion and cracking
● the formation of gypsum (calcium sulphate dihydrate), leading to softening
and loss of concrete strength

Protection against sulphate attack can be achieved by using concrete with low
permeability, using cements with a low C3A content and blends of PC with pozzolans
(Khatib et al., 2008; Mangat and El-Khatib, 1992; Mangat and Khatib, 1995) (thus
reducing the available Ca[OH]2). Proper placement, compaction, finishing, and
curing of concrete are essential to minimise the ingress and movement of water,
which is the carrier of the aggressive salts. Krammart and Tangtermsirikul (2004)
indicated that the expansions of municipal solid waste ashes and calcium carbide
waste cements in sodium sulphate solution were lower than that of the control
cement when exposed to sulphate solution.

There are many factors affecting sulphate attack and steps to mitigate it. In gen-
eral, three approaches are adopted: (a) preventing sulphates from penetrating into
concrete; (b) consuming Ca(OH)2 as much as possible in hydrated cement matrix
through the use of pozzolana such as PFA and GGBS; and (c) using cement with low
C3A.

The first approach is very important and can be achieved by producing impermeable
concrete so as to stop or slow the penetration of sulphates into concrete, thus to
extend the concrete service life. For concrete structures which are in contact with
sulphate-bearing soils, protective linings such as the various proprietary self-adhe-
sive membranes, or protective coatings, such as bitumens, tars and epoxy resins,
may also be applied on exterior surfaces.

Pozzolans such as PFA (Chindaprasirt et al., 2004; Zuquan et al., 2007), silica fume
(Ganjian and Pouya, 2005; Roy et al., 2001), MK (Hossack and Thomas, 2015; Khatib
and Hibbert, 2005; Sabir et al., 2001) and GGBS (Gollop and Taylor, 1996; Higgins,
2003) can be employed to effect improvement in the resistance of concrete to
sulphate attack. The effect of pozzolana is that the pozzolanic reactions consume
Ca(OH)2, which is needed for reaction with sulphates. In the meantime, blended
cement concrete has less Ca(OH)2 due to the replacement of cement with pozzolana.

Finally, the formation of ettringite can be minimised by using sulphate-resisting

cement, which has lower C3A content. This in turn will reduce the expansive ettringite
formation.
> Read full chapter

Environmentally Assisted Fatigue

G.K. Glass, in Comprehensive Structural Integrity, 2003

6.07.3.2 Sulfate Attack

Sulfate attack results from the deleterious chemical reaction between soluble sulfates
and the constituents of cement. The reaction products produced occupy a greater
volume than the compounds they replace and the binder (cement paste) may be
destroyed; thus, expansion and disruption of the concrete may result. Examples
of sulfate attack include ettringite formation, delayed ettringite formation, and
thaumasite formation (Hobbs, 2001).

Ettringite or hydrated calcium aluminum sulfate hydroxide (Ca6Al2(SO4)3(OH)12-

·26H2O) is formed by the reaction between sulfate ions and the aluminate phases in
cement. It forms naturally during cement hydration as calcium sulfate is included in
the mix materials to control hydration. It is an expansive product but deterioration
only results when it forms after the cement has hardened.

The natural formation of ettringite during hydration may be delayed if the concrete
temperature rises to values above 65°C while the cement paste is setting. The
subsequent internal expansion that arises from delayed ettringite formation results
in cracking of the concrete. The heat, which gives rise to the problem, may arise
from the exothermic hydration reactions or the curing regime applied (e.g., steam
curing). These problems should be solved by appropriate design.

A more common form of sulfate attack of concrete occurs when sulfates from
an external source penetrate the concrete and produce ettringite. Sulfates may
be present in ground water, canals, and sewers. The deterioration starts from the
surface. Edges and corners are particularly vulnerable, and a friable concrete surface
results (Figure 8).
Figure 8. Deterioration of a reinforced concrete tank arising from the external
ingress of sulfate ions (courtesy of Taywood Engineering Ltd.)

Thaumasite is a calcium silicate carbonate sulfate hydrate (Ca3Si(OH)6CO3SO4·12H-

2O) formed by sulfate attack of concrete or mortar. It is usually found in cold wet

conditions encountered in buried concrete and a source of sulfate, carbonate, and

water are required. Thaumasite is often found in concrete containing limestone as an
aggregate which may provide the source for the carbonate ions. It grows expansively
and both the cement paste and aggregate are attacked. It is an unusual form of
deterioration affecting a limited number of structures.

Various guidelines have been produced to assist in the detection of environments

associated with a high risk of deterioration and the steps to take to avoid such dete-
rioration (BCA, 2001). Such steps include the use of coatings and resistant cement
types. Existing damage may be repaired replacing the damaged concrete. This may
be complimented with a barrier coating to prevent further sulfate contamination.

> Read full chapter

Causes and mechanisms of deteriora-

tion in reinforced concrete
V. Penttala, in Failure, Distress and Repair of Concrete Structures, 2009

Sulfate attack
Sulfate attack is initiated when water-soluble sulfates (SO42–), originating from
ground or from seawater, penetrate into concrete pore water and react with alumi-
nates or calcium hydroxide in cement paste. Reaction products expand remarkably
which causes crack propagation and decreases the strength properties of concrete.
Four reaction mechanisms are responsible for sulfate damage in concrete. Sulfate
ions can react with calcium hydroxide forming gypsum (CaSO4 · H2O). Aluminates
from cement or sometimes from aggregates can react with sulfates forming trisul-
fate (ettringite 3CaO · Al2O3 · 3CaSO4 · 31H2O). The increase in volume of the solid
phases in these reactions is 124 and 227%, respectively.

The third sulfate deterioration mechanism is attributed to sulfate absorption into

silicates or to a reaction with C–S–H. In these instances thaumasite (CaSiO3 · CaCO-
3 · CaSO4 · 15H2O) is produced. This reaction takes place at low temperatures

(Schneider et al., 2003; Mielich and Öttl, 2004). The fourth mechanism does not
need an outside source of sulfates to cause expansion and cracking into concrete.
The deterioration mechanism can be termed inner sulfate attack caused by excessive
heat treatment in concretes produced by Portland cement. When the temperature
rises to 70–100 °C during hydration, ettringite transforms into monosulfate (3CaO-
 · Al2O3 · CaSO4 · 12H2O) and sulfate. At lower temperatures, monosulfate becomes
metastable and, if there is sufficient water available in hardened concrete or if
the water content in the concrete subsequently increases, ettringite can again be
formed. This reaction is accompanied by expansion in the concrete structure and
subsequent cracking. This reaction can happen after a period of a couple years and,
therefore, it is sometimes called delayed ettringite formation (Heinz, 1989; Stark et
al., 1992). This deterioration mechanism has been observed in façade precast units,
concrete railway sleepers, and basement slabs.

The severity of sulfate corrosion expansion caused by outside sulfate attack is differ-
ent depending on the salt composition. The severity increases in the order calcium
sulfate, sodium sulfate, and magnesium sulfate. The severity of the attack increases
also when the moisture content in concrete increases.

Sulfate attack can be mitigated by minimizing the C3A content of the cement by
applying sulfate resisting cements (Fig. 1.8). Sulfate resisting cements have a C3A
content below 3% or blast furnace slag content in the binder exceeds 70%. The other
mitigation method is to reduce the Ca(OH)2 content in concrete by applying blended
cements in which the pozzolanic reaction decreases the calcium hydroxide amount.
 1.8. Sulfate expansions of test mortars produced by different binders. The water :
cement ratio of the mortars is 0.6, mortars have been immersed in sodium sulfate
solution in which SO4–2 content is 30 g/l (Frearson, 1986). The author has introduced
contemporary cement-type notations into the figure.

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