IntroductIon

Concrete exposed to sulfate solutions can be

attacked and may suffer deterioration to an
extent dependent on the concrete constituents,
the quality of the concrete in place and the
type and concentration of the sulfate.
Knowledge of the sulfate-resisting
characteristics of concrete is necessary so that
the appropriate steps can be taken to minimise
the deterioration of concrete exposed to sulfate
solutions.
For many years, sulfate-resisting cement was
specified in terms of its chemical constituents.
In recent years, sulfate-resisting cement has
been characterised by its sulfate-resisting
performance and has been included in AS 3972.
This article reviews the factors affecting sulfate
resistance of concrete, seeking to put in
perspective their varying influences and thus
enabling practical and effective measures be
taken to produce sulfate-resisting concrete.
Sulfate attack on concrete
occurrence Naturally occurring sulfates of
sodium, potassium, calcium or magnesium are
sometimes found in soil or dissolved in ground
water or present in aggregates (eg pyrite). Sulfate
may be present in industrial effuents and
wastes such as in industries associated with the
manufacture of chemicals, batteries, aluminium
and in the mining industry. The water used in
cooling towers may also contain sulfates because of
the gradual build-up of sulfates from evaporation.
Mechanism There are two chemical reactions
involved in sulfate attack on concrete:
1 Reaction of the sulfate with calcium hydroxide
liberated during the hydration of the cement,
forming calcium sulfate (gypsum).
2 Reaction of the calcium sulfate with the
hydrated calcium aluminate, forming calcium
sulphoaluminate (ettringite).
Both of these reactions result in an
increase in the volume of solids which is
the cause of expansion and disruption of
concretes exposed to sulfate solutions.
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sulfate-resisting Cement
and Concrete
SulFATe mAy Be pReSeNT in
industrial effluents and wastes
such as in industries associated
with the manufacture of chemicals,
batteries, aluminium and in the
mining industry.
>
JULY
2002
Page 2 of 5 > sULfate-resisting Cement and Concrete
It should be pointed out that sulfates and
chemicals in general rarely, if ever, attack concrete
if they are in a solid or dry form. To result in
signifcant attack on concrete, sulfates must be in
solution and above some minimum concentration.
The severity of sulfate attack on concrete depends
on the following:
Type of sulfate; magnesium and ammonium
sulfates are the most-damaging to concrete.
Concentration of the sulfate; the present of
more-soluble sulfates is more damaging to
concrete. most recommendations take into
account the amount of sulfate present in
classifying the severity of the attack table 1.
Whether the sulfate solution is stagnant or
fowing; severity of the attack increases in the
case of fowing waters. Thus the nature of the
contact between the sulfate and the concrete is
important. more intensive attack takes place on
concrete which is exposed to cycles of wetting
and drying than on concrete which is fully and
continuously submerged in the solution.
pressure; severity of the attack increases
because pressures tend to force the sulfate
solution into the concrete.
Temperature; as with any chemical reaction, the
rate of the reaction increases with temperature.
presence of other ions; other ions present in the
sulfate solution affect the severity of the attack.
A typical example is seawater which contains
sulfates and chlorides. It is generally found that
the presence of chloride ions alters the extent
and nature of the chemical reaction so that less
expansion is produced in concrete due to the
sulfates in seawater.
As can be seen, the intensity of the sulfate
attack is a complex question which is infuenced by
many factors. In practice, however, it is diffcult to
consider all the factors involved and in most cases,
the severity of the attack is related mainly to the
sulfate concentration and the means for combating
it are specifed accordingly.
factorS affectIng Sulfate reSIStance of
concrete
Sulfate attack on concrete will take place when the
sulfate solution penetrates the concrete and
chemically reacts with its constituents, mainly the
cement matrix. Thus, factors affecting sulfate
resistance of concrete are not only those infuencing
the chemical reaction with the cement matrix, but
also those infuencing the permeability and the
overall quality of the concrete.
cements
The relationship between sulfate resistance of
portland cement and its tricalcium aluminate (C
3
A)
content is well established
(1)
. portland cement
containing less than 5% C
3
A has been classifed as
sulfate-resisting cement and used as the
specifcation criterion in many codes and standards
for cement all over the world, including the
Australian Standards until relatively recently
(2)
.
Studies have shown that cements potentially
containing less calcium hydroxide on hydration
perform well in sulfate exposure, eg certain
portland/blast furnace slag cements and portland/
fy ash cements(
(3,4)
. The effectiveness of these
cements in enhancing the sulfate resistance of
concrete has been the subject of extensive work
and many explanations for the improvement have
been offered.
It was recognised that a limit on C
3
A content for
these cements is neither appropriate nor applicable
and that a reliable performance test method and
associated criteria are required to characterise
cements in terms of their performance. As part of
the development of the Australian Standard AS 3972
as a performance-based specifcation for portland
and blended cements, the cement industry, under
the auspices of Standards Australia Committee
BD/10, completed an extensive investigation which
resulted in replacing the limit on C
3
A for sulfate
resisting (Type SR) portland cement by a
performance test and a performance limit suitable
for Type SR cement, being either portland or
blended cement
(2)
.
table 1 Recommendations for concrete exposed to sulfates
Sulfate concentration, So
4
2
Min curing Min concrete
Min cement equivalent added cover to
in water in soil cement Max content moist curing protection reinforcement
(mg/l) (%) type w-c ratio (kg/m
3
) (days) needed? (mm)
<400 <0.4 Gp, GB 0.55 300 3 No 50
400600 0.40.6 Gp, GB 0.5 330 3 No 50
SR 0.55 300 7 No 50
6003000 0.51.2 SR 0.5 330 7 No 65
30006000 1.22.0 SR 0.45 370 7 No 65
>6000 >2.0 SR 0.45 370 7 yes 50
Page 3 of 5 > sULfate-resisting Cement and Concrete
A standard test method for measuring
expansion of a standard mortar prism exposed to a
standard sodium sulfate solution for an extended
period of time has been established and is
published as AS 2350.14. A maximum limit for
expansion after 16 weeks of sulfate exposure is set
at 900 microstrain for Type SR cement. This
maximum limit takes into account not only the
performance of the cement but also the precision of
the test method. The precision of the test method is
such that the difference between two test results for
the expansion after 16 weeks of exposure to a
standard sodium sulfate solution, obtained in two
different but experienced laboratories under
conditions of reproducibility, may be expected
(probability of 95%) to be up to 300 microstrain. This
maximum limit for expansion implies that it must
not be exceeded by one or any result. For example,
a sulfate resisting cement could have an average, or
target, expansion at 16 weeks of 600 microstrain or
less so that a single result obtained in a different
laboratory may not exceed the maximum limit set in
the Standard.
Caution should be exercised in interpreting the
expansion results. The test method is inherently of
lower precision than other performance tests,
eg strength or drying shrinkage. Thus, for example,
a cement producing an average expansion result of
500 microstrain may bot be of a signifcantly better
performance than another cement with an average
expansion result of 600 microstrain.
It should be pointed out that the use of Type SR
cement alone will not guarantee the production of
sulfate resisting concrete. As outlined in this article,
other factors are involved and should be considered
as their effect may outweigh the effect of cement on
the sulfate resistance of concrete.
cement content
Cement content of concrete signifcantly affects its
sulfate resistance, regardless of the composition of
the cement as is evident from figures 1 and 2.
The data presented in these fgures represent a
range of portland and blended cements. The rate of
deterioration decreases with increase in cement
content, even in concretes made of ordinary
portland cement. In other words, to produce sulfate
resisting concrete, the use of sulfate resisting
cement should be combined with the use of a
minimum cement content. This conclusion is
refected in recommendations to produce sulfate
resisting concrete
(5)
table 1.
Water-cement ratio
low permeability of the concrete is a signifcant
factor infuencing its resistance to sulfate attack.
Given good quality materials, satisfactory
proportioning and good concrete practice, the
permeability of the concrete is a direct function of
its water-cement ratio and the curing time. In other
words, all other factors being equal, sulfate
figure 1: effect of different portland cements and
cement contents on rate of deterioration of concrete
exposed to sulfate-bearing soils (after Verbeck)
6
figure 2: effect of different portland and blended
cements and cement contents on expansion of
concrete exposed to sulfate solution
Severity of sulfate attack depends on type and
concentration of the sulfate and increases with
wetting and drying
R
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R
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C
3
A CONTENT (%)
0
1 2 3 4 Cement:
C
e
m
e
n
t

c
o
n
t
e
n
t

(
k
g
/
m
3 )

=

2
2
5
3
1
0
390
4 2 6 8 10 12
A
V
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R
A
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E

E
X
P
A
N
S
I
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N
CEMENT
C1 C3 C2 C4
280 = Cement content (kg/m
3
)
330
370
Page 4 of 5 > sULfate-resisting Cement and Concrete
resistance of concrete increases with decreases in
its water-cement ratio. This effect of water-cement
ratio is shown in figure 3 which is based on data
obtained from exposure tests
(6)
.
admixtures
There are many types of admixtures available for
incorporation in concrete to enhance certain
properties, or to achieve economy, or both.
Generally, the effect of admixtures on concrete
properties depends not only on their formulation
and their interaction with the cement, but also on
the variations or adjustments they bring about in
the proportions of the concrete mix. Thus,
admixtures that effect reduction in water-cement
ratio and/or increased workability can enhance the
sulfate resistance of concrete, provided they are not
used to reduce its cement content.
It is well established that admixtures containing
calcium chloride adversely affect the sulfate
resistance of concrete
(7)
.
construction practice
Concrete placing, compaction and curing are
important factors in producing low-permeability
concrete. Adding further water on site during
placing of concrete to restore slump or to aid with
the fnal fnishing will impair the sulfate resistance
of concrete. Adequate compaction and proper
curing are required to produce dense concrete with
discontinuous capillaries (low permeability).
Finishing of the concrete to provide a dense
smooth surface, free of holes and defects can
enhance the concrete resistance to sulfate.
design and detailing
properly designed and detailed structures and
elements should provide for adequate
reinforcement, correctly located to minimise
cracking. Detailing to minimise ponding and/or
areas of turbulence is important in reducing the
intensity of the sulfate attack, thus enhancing the
sulfate resistance of the concrete.
Sulfate reSIStIng concrete
From the previous discussion it may be said that
sulfate resistance of concrete can be signifcantly
improved by producing dense impermeable
concrete made of sulfate resisting cement, of low
water-cement ratio, with suffcient cement content,
which is properly placed, compacted and cured.
Various authorities have classifed
aggressiveness into a number of categories of
increasing severity
(5,8)
. Considering this
classifcation and the types of cement currently
available, table 1 gives recommendations for
concrete exposed to fve classes of sulfates of
increasing severity.
In using this table, a number of points should be
borne in mind:
In view of the many factors affecting the
intensity of sulfate attack and the many factors
infuencing the sulfate resistance of concrete, as
discussed earlier, these classifcations and
recommendations should be regarded as
guidelines and must be examined in relation to
the particular conditions met in practice. The
presence of acidic conditions as in the case of
sulfuric acid, may require additional measures
to be taken such as the provision of membranes
and protective barriers, depending on concentr-
ation and temperature of the aggressive
solution. Also, magnesium sulfate is more
aggressive than sodium sulfate. In the presence
of high amounts of magnesium ions (>1000 mg/l)
additional measures may need to be taken
(5)
.
As mentioned earlier, Type SR cement can be
portland or blended cement complying with the
performance requirements of AS 3972. Blended
cements may contain fy ash or slag or silica
fume or a combination of these.
figure 3: effect of w-c ratio on rate of deterioration
of concrete exposed to sulfate-bearing soils (after
Verbeck)
6
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WATER TO CEMENT RATIO
0.4 0.5 0.6 0.7 0.8
Concrete footing attacked by sulfates in soil.
Soil contained 3.8% soluble sulfates
Page 5 of 5 > sULfate-resisting Cement and Concrete
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concluSIon
The importance of the many infuences on the
sulfate resistance of concrete cannot be too highly
emphasised. Whilst the infuence of the cement
type is important, obviously it is not the only
infuence. Indeed, in most situations other factors
will have an equal if not over-riding infuence. It is
the mix design of concrete; reduced water content,
increased cement content, proper placing, adequate
consolidation and effective curing that will produce
sulfate resisting concrete.
referenceS
1 mather, B field and laboratory studies of the
sulfate resistance of Concrete pCA
laboratories Research Bulletin, No. 227, 1968.
2 AS 3972 Portland and Blended Cements
Standards Australia, 1997.
3 mehta, p K Concrete structures, Properties
and Materials prentice Hall, Inc, englewood
Cliffs, New Jersey, 1986, pp 119129.
4 Oberholster, Van Aardt J H and Brandt, m
Durability of Cementitious systems structures
and performance of Cements ed p Barnes,
Applied Science publishers, 1983, pp 365413.
5 sulfate and acid resistance of Concrete in the
ground Building Research establishment BRe
Digest 363, January 1996.
6 Verbeck, G field and laboratory studies of the
sulfate resistance of Concrete performance of
Concrete, ed. e G Swenson, National Research
Council of Canada and the American Concrete
Institute, 1967.
7 popovics, S Concrete Materials Properties,
specifcations and testing Second edition,
pp 221271, Noyes publications, 1992.
8 ACI Committee 201 guide to Durable Concrete
ACI manual of Concrete practice, part 1, 2001.
Further information on good concreting
practices can be downloaded from the Cement
Concrete and Aggregates Australia website at
www.concrete.net.au.
JULY
2002