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Sulfate Attack
sulfate attack involving expansive ettringite formation along with other reactions, in which the
sulfate is introduced principally from the external environment
From: Durability of Concrete and Cement Composites, 2007
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Deterioration processes in reinforced
concrete: an overview
D. Breysse, in Non-Destructive Evaluation of Reinforced Concrete
Structures: Deterioration 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).
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3.7. Cracking pattern in a bridge suffering from internal sulfatic attack (from Germain, 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.
View chapter Purchase book
Microscopic examination of deteriorated
concrete
T.G. Nijland, J.A. Larbi, in Non-Destructive Evaluation of Reinforced
Concrete Structures: 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 conditions. 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.
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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 exudations. In the laboratory,
diagnosis of cores removed from structures affected by sulfate attack
begins with a visual inspection, using a hand lens or a
stereomicroscope. 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.
View chapter Purchase book
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 general, 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-adhesive 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.
View chapter Purchase book
Concrete Aggregates
Ian Sims, ... James Ferrari, in Lea's Chemistry of Cement and
Concrete (Fifth Edition), 2019
15.6.8.2 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
Figg,263 Eglinton264 and Bensted262; more extensive treatments may
be found in Swenson,265 American Concrete Institute266 and Poole
and Sims.93
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 ISA, and many such materials have given rise to
problems in the Middle East.15,18,84,267. Particles of gypsum present
in natural sands from Bahrain, for example, were observed by
Hussen267 to react within concrete, forming calcium hydroxide
(portlandite) and ettringite. Samarai,268 in experiments in Iraq using
powdered gypsum in mortar bars, produced unacceptably high
expansions with Portland cement concrete mixtures containing total
sulfate contents in excess of 5% by mass of cement.
French and Crammond269 identified the cause of expansion of
concrete and mortar made with serpentinite wadi aggregates from
the United Arab Emirates as being internal sulfate attack (ISA)
involving contamination of the aggregate by up to 5% coarsely
crystalline gypsum (Fig. 15.35), and later work by Crammond88 found
that up to 2.5% coarsely crystalline gypsum (or about 6% total sulfate
by mass of cement) could be tolerated for Portland cement concrete
(Fig. 15.36).
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Fig. 15.35. Scanning electron photomicrograph of internal sulfate attack in concrete from the Arabian Gulf area. 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.
(From French WJ, Crammond NJ. The influence of serpentinite and other rocks on the stability of concretes in the Middle
East. Quart J Eng Geol 1980;13(4):255–80.)
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Fig. 15.36. 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
temperature of 20°C.
(Courtesy Building Research Establishment. Crown copyright 1990.)
In rare cases, pyrite (iron disulfide), or especially the less stable
pyrrhotite (see Section 15.4.4), in aggregate can decompose in
concrete in a complicated series of reactions with cement to form
gypsum, ettringite and other compounds with accompanying
expansion.89,270 Other aggregates may themselves be vulnerable to
sulfate attack; Braga Reis,271 for example, has described expansive
ettringite formation as the result of reactions between sulfates and
kaolinised feldspar in a weathered granite aggregate.
Some documented cases worldwide,272–275 reported that a particular
form of sulfate attack had occurred in concrete that had been
designed to resist sulfates. In these limited cases, a different reaction
product, thaumasite (CaSiO3·CaCO3·CaSO4·15H2O) had been
formed instead of the gypsum (CaSO4·2H2O) and ettringite
(3CaO·Al2O3·3CaSO4·32H2O) 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.
This thaumasite form of sulfate attack (‘TSA’) appeared more likely to
occur in consistently wet and cooler conditions and, in its worst case,
was found to cause concrete to decay into a mush-like form, losing
its strength and integrity. Moreover, as the formation of thaumasite
involves reaction with the silicate rather than aluminate components
of hardened cement, the use of SRPC, which relies on containing less
aluminate phase (and more ferrite instead), is ineffective in
preventing TSA.
Thaumasite occurs as needle-like crystals, similar in appearance to
ettringite, and analytical methods to determine sulfate contents of
concrete are unable to distinguish between the two different forms of
attack, respectively, leading to ettringite and thaumasite.
Differentiation between these two forms requires microscopical
and/or X-ray diffraction methods. Crammond and Halliwell274
highlighted 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.
Although TSA had long been recognised by concrete petrographers as
an unusual deteriorative mechanism274a investigation into severely
degraded buried concrete elements of some motorway bridges in
south-west England in 1998 (Fig. 15.37) confirmed its destructive
potential and led to an urgent research programme, led by Professor
Leslie Clark.276 Clark’s thorough report identified various primary and
secondary factors associated with the risk of TSA and one of the four
primary risk factors was the ‘presence of carbonate, generally in the
concrete aggregates’.
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Fig. 15.37. Extreme example of TSA in a concrete bridge column that had been buried in sulfate-rich ground.
(From DETR. The thaumasite form of sulfate attack: risks, diagnosis, remedial works and guidance on new construction. Report of
the Thaumasite Expert Group (TEG). London, UK: Department for the Environment, Transport and the Regions (DETR); 1999.)
As a result, the preliminary guidance for minimising the risk of TSA
deterioration in buried concrete, in contact with ground exhibiting
sulfate Classes 3–5,277,278 advocated restrictions on the content of
carbonate from aggregates, including coarse and fine crushed
limestones and/or limestone-bearing sands and gravels. The total
aggregate contribution to the carbonate content of a concrete was
resolved into three ranges (A highest, B and C lowest), depending on
the calcium carbonate content of the total aggregate and the
proportion of that total that was present in the fine aggregate
fraction. This approach was incorporated into the initial revision of
the BRE (‘Special’) Digest on ‘Concrete in Aggressive Ground’,277 but
there was always concern that the carbonate necessary for TSA was
frequently available from alternative sources and these carbonate
ranges for aggregates were later withdrawn and do not feature in the
current edition of the Digest.279 Further information on TSA may be
found in Poole and Sims.93
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The resistance of alkali-activated cement-
based binders to chemical attack
Z. Baščarevć, in Handbook of Alkali-Activated Cements, Mortars and
Concretes, 2015
14.2.1 Background
External sulphate attack refers to the deterioration of a binder
material resulting from chemical reactions occurring when a binder
is exposed to a solution containing a high concentration of dissolved
sulphates. Foundations and/or parts of structures in contact with
groundwater and soils in arid regions or concrete in contact with
wastewaters may be subject to sulphate attack (Alexander et al., 2013).
Upon contact of hydrated Portland cement with sulphate solution,
diffusion of sulphate ions into the structure of the hardened cement
occurs. Diffusion is followed by reactions of sulphate ions with some
of the phases present in the structure. The main reaction products of
sulphate attack on hydrated Portland cement are gypsum, ettringite,
thaumasite or mixtures of these phases (Glasser et al., 2008). The
formation of these phases can cause expansion, stress, strength loss,
and finally deterioration of the material. Occurrence and the extent of
deterioration of hardened Portland cement structure in contact with
a sulphate solution depend on the type of Portland cement,
water/binder ratio, pH of the sulphate solution, concentration of
sulphate ions, type of cation accompanying the sulphate ions,
temperature, etc. (Neville, 2004; Santhanam et al., 2001; Messad et
al., 2009).
Although there are numerous investigations on the effects of
sulphate solutions on hydrated Portland cement structures (Neville,
2004), at the moment, there is no standard method in Europe for
testing the resistance of cementitious materials to sulphate attack
(CEN/TR 15697:2009). Probably the most widely used test procedure
for assessment of sulphate resistance of ordinary and blended
Portland cement is ASTM C1012. This standard uses expansion of
25 × 25 × 285 mm mortar bars, after the immersion in 50 g/L
solution of sodium sulphate, as a measure for evaluation of sulphate
resistance of Portland cement. Several other sulphate resistance
testing procedures are often used, such as Koch-Steinegger, SVA,
Wittekind, etc. (see CEN/TR 15697:2009 and Alexander et al., 2013,
for detailed discussion on sulphate resistance test methods).
Due to generally lower content of calcium in alkali-activated binders
than in hydrated Portland cement, it should be expected that the
mechanism of sulphate attack on alkali-activated binders is different.
Therefore, some test parameters used to assess sulphate resistance of
Portland cement should probably be modified in order to provide a
proper evaluation of resistance of alkali-activated binders to sulphate
attack (Bernal and Provis, 2014). Currently, there is an ongoing work
of RILEM Technical Committee DTA: Durability testing of alkali-
activated materials on providing recommendations regarding
appropriate test methodologies for testing durability of alkali-
activated binders. One of the areas which will be given special
attention is sulphate attack on alkali-activated binders.
The following subsections will provide an overview on previous work
done on investigating sulphate attack on alkali-activated binders. The
review is roughly divided into three subsections, according to the
chemistry of the alkali-activated binders. High-calcium alkali-
activated binders are usually obtained from calcium-rich starting
materials, such as granulated blast furnace slag. Although alkali-
activated binders based on blends of blast furnace slag and an
aluminosilicate material, such as fly ash, have intermediate calcium
content, sulphate resistance of these materials has also been analysed
in the subsection dealing with high-Ca alkali-activated binders. The
second subsection will be focused on sulphate resistance of low-
calcium alkali-activated binders, based on aluminosilicate source
materials, such as fly ash and metakaolin. Some results on sulphate
resistance of hybrid Portland cement–alkali-activated aluminosilicate
systems will be given in the third subsection.
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Related terms:
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Supplementary cementing materials
Daman K. Panesar, in Developments in the Formulation and
Reinforcement of Concrete (Second Edition), 2019
3.6.4 Sulfate attack
Sulfate attack of concrete is a complex process, which includes
physical salt attack due to salt crystallization and chemical sulfate
attack by sulfates from soil, groundwater, or seawater. Sulfate attack
can lead to expansion, cracking, strength loss, and disintegration of
the concrete. Sulfate attack is generally attributed to the reaction of
sulfate ions with calcium hydroxide and calcium aluminate hydrate to
form gypsum and ettringite. The formation of ettringite leads to an
increase in solid volume, resulting in expansion, cracking, and mass
loss, particularly when restrained. The formation of gypsum can lead
to softening and loss of mass and strength. In addition to the
formation of ettringite and gypsum and its subsequent expansion,
the deterioration due to sulfate attack is partially caused by the
degradation of the calcium silicate hydrate through leaching calcium
compounds. This process leads to loss in calcium silicate hydrate gel
stiffness and an overall deterioration of the cement paste matrix.
There is a general consensus that the use of fly ash, slag cement,
silica fume, and metakaolin can reduce the expansion and damage
due to sulfate attack (Juenger & Siddique, 2015; Ramezanianpour &
Hooton, 2013). Although sulfate resistance depends on the
characteristics of the SCMs, their use in concrete can improve sulfate
resistance by (1) the occurrence of pozzolanic reactions that consume
the calcium hydroxide, making it unavailable to react with sulfate to
form ettringite, (2) reduced reactive aluminates in the system, and (3)
reduced permeability that aids to bar the penetration of harmful
sulfate ions into the concrete (ACI-Committee-233, 2017).
Silica fume is effective in reducing or preventing attack from sodium
sulfate, mainly by its role in reducing permeability, as well as
reducing the calcium hydroxide content due to pozzolanic reactions
(Bonen & Cohen, 1992; Cohen & Bentur, 1988). The use of
metakaolin as cement replacement in concrete generally increases
resistance to aggressive attack by sulfates (Al-Akhras, 2006; Khatib &
Wild, 1998) because of the corresponding densified microstructure
and lower permeability. In fact, it has been reported that by
increasing the percentage of metakaolin from 10% to 20% cement
replacement reduces the expansion, greater than when less than 10%
metakaolin is used (De Belie et al., 2017).
View chapter Purchase book
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 expansions 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).
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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.
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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
temperature 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
ettringite 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·CaSO4·15H2O) 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.
View chapter Purchase book
Durability of sustainable concrete materials
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 penetrating 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.
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Causes and mechanisms of deterioration 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 aluminates 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 trisulfate (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 · CaCO3 · 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 different 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.
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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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Chemical durability of geopolymers
A. Fernández-Jiménez, A. Palomo, in Geopolymers, 2009
9.2 Sulphate attack and sea water attack resistance
Sulphate attack can occur when cement is attacked by solutions
containing sulphates, such as some natural or polluted ground
waters. In OPC this type of attack can lead to strength loss,
expansion, spalling of surface layers, and ultimately disintegration
(Taylor 1994, Taylor and Gollop 1997, Neville 1995). However, in the
case of alkaline inorganic polymer cements, including alkali activated
metakaolin and fly ash; numerous references found in the literature
show that this type of material displays very good resistance to
conventional sulphate attack and sea water due to the absence of
high-calcium phases.
Palomo et al. (1999b) reported that mortars made with alkali-
activated metakaolin show very good stability when immersed in
various types of aggressive solutions: deionised water, ASTM
seawater, sodium sulphate solution (4.4% wt.) and sulphuric acid
(0.001 M). It was observed that the nature of the aggressive solution
had little negative effect on the evolution of microstructure and the
strength of these materials. Only some fluctuations in flexural
strength were observed between 7 days and 3 months of immersion
(independent of the type of aggressive agent), which were considered
to be due to a dissolution-precipitation phenomenon that occurs
during this period. Clearly, this process has a negative influence on
the development of mechanical strength. The transformation of the
amorphous aluminosilicate network into a crystalline structure can be
partly attributed to the duration of the treatment (immersion). While
representing a relatively small proportion of these crystals, faujasites
– which would appear to reinforce the cement matrix – account for
the steady increase in its mechanical strength after 90 days of
immersion.
Bakharev (2005a), in turn, sustained that the stability of alkali-
activated fly ash pastes in aggressive environments (5% solution of
sodium sulphate, 5% solution of magnesium sulphate and a mixture
of both solutions) depended on the intrinsic ordering of the
components within the aluminosilicate gel. She also observed some
fluctuations of strength in all materials studied (see Fig. 9.1) that
were linked to migration of alkalis from the geopolymer into
solution. She found that geopolymer materials prepared with sodium
hydroxide are more crystalline than when prepared with sodium
silicate activators. The greater the crystallinity, the more stable were
the geopolymers in aggressive environments. She attributed these
findings to the formation of a more stable cross-linked
aluminosilicate polymer structure when the activator used was
sodium hydroxide. In any event, alkali-activated fly ash mortar was
observed to perform better than ordinary Portland cement pastes and
no visual signs of deterioration were observed.
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9.1. Compressive strength evolution of fly ash activated with NaOH and with sodium silicate solution, and Portland cement
specimens, exposed to 5% sodium and magnesium sulphate solutions.
Data obtained from Bakharev (2005a)
Similar behaviour was observed more recently by Fernández-Jiménez
et al. (2007). They found that the materials did not deteriorate
significantly, with mechanical strength increasing over time
irrespective of the medium in which the specimens were immersed
(air, water, 4.4% sodium sulphate solution, ASTM seawater), see Fig.
9.2. These results also show that mechanical strength fluctuated in
the early ages in all media. Those authors considered that these
fluctuations should not be solely attributed to the medium in which
the samples were immersed, since they were also detected in the
control specimens (cured under laboratory conditions, air). The
reasons for such variations, also observed by the other authors, are
not clear and will be addressed in greater detail in the near future.
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9.2. Compressive strength evolution of (a) fly ash mortars activated with an 8M NaOH solution, and (b) mortars activated
with a sodium silicate solution (waterglass). Samples were held under laboratory conditions (air), and immersed in
desionised water, 4.4% sodium sulphate solution, and ASTM seawater.
Data obtained from Fernández-Jiménez et al. (2007)
All the results obtained by the different authors (Bakharev 2005a,
Fernández-Jiménez et al. 2007) show that alkaline activated fly ash
pastes and mortars perform satisfactorily when exposed to sulphates
and seawater. No significant differences were observed in gel
composition or microstructure after contact with saline solutions.
Nonetheless, the presence of sodium sulphate was detected in some
cases, but this is associated less with the degradation of the matrix
than with the inward migration of sulphate ions through its porous
structure. Owing to the large amount of Na in the system, these
sulphate ions precipitate into the gaps or pores in the matrix in the
form of sodium sulphate. In the specimens immersed in seawater,
magnesium ions in the solution also were observed to seep into the
matrix. In this case, since the process appears to involve the exchange
of Mg and Na ions, it introduces changes in gel composition and
morphology. A silicon-rich gel with some magnesium was observed
to appear sporadically in the specimens immersed in seawater. These
reactions are very sporadic, however, and seem to have no significant
effect on mechanical strength.
The performance differences in durability tests depending on the
activator used (NaOH or sodium silicate) are due in part to the
structural variations in the alkaline silicoaluminate gel formed as a
result of the different Si/Al ratios induced in the system, as well as to
the larger or smaller amounts of (zeolitic) crystalline phases in the
matrix. It is known that the presence of soluble silicates in the
activating solution generally reduces the degree of alkaline
silicoaluminate crystallisation and retards zeolite crystallisation
(Engelhardt and Michel 1987, Klinowski 1984). Moreover, the
presence of silicate ions leads to the formation of more compact
structures, with gels richer in Si (Duxson et al. 2005, Fernández-
Jiménez and Palomo 2005b, Fernández-Jiménez et al. 2006, Criado et
al. 2007). This would explain why mechanical strength is higher in
mortars activated with sodium silicate solution than with NaOH.
Li et al. (2005) indicate that only a small extent of shrinkage was
observed in prisms of geopolymer mortar (derived from metakaolin)
immersed in 0.31 M Na2SO3 solution. However, in similar
conditions, OPC mortar prisms displayed a large expansion.
Sulphate attack in concrete or mortar based on Portland cement is
generally attributed to the formation of expansive ettringite (AFt-
phase) and gypsum. The sulphate ions intrude into the concrete and
react with portlandite Ca(OH)2 to generate gypsum. With the
presence of sufficient sulphate, the metastable
monosulphoaluminate transforms into ettringite. This ettringite then
absorbs moisture to generate expansion and results in local
disruption of the matrix. The more voluminous gypsum and
ettringite formed as a result of sulphate attack are the cause of
expansion cracking and spalling (Malek and Roy 1997, Taylor 1994,
Taylor and Gollop 1997). Geopolymer products do not in general
contain Ca(OH)2 and monosulphoaluminate due to being formed
from source materials containing little or no calcium. So, when these
materials are exposed to sodium sulphate solution, there is no
growth of gypsum and ettringite in the matrix to cause expansion,
meaning that geopolymer mortar cannot be corroded by sulphate
attack according to these mechanisms.
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