PCA R&D Serial No.

2916a

Sulfate Resistance of Concrete Using

Blended Cements or Supplementary
Cementitious Materials

by Javed I. Bhatty and Peter C. Taylor

©Portland Cement Association 2006

All rights reserved
KEYWORDS
Sulfate attack, mechanism, sulfate resistance, supplementary cementitious materials (SCMs), fly
ash, ground granulated blast furnace slag (GGBFS), silica fume, blended cements, interground
SCMs, cement chemistry, SCMs chemistry, reactivity, sulfate resistant models, sulfate attack
prediction, R factor, calcium aluminate potential factor (CAP), oxide durability factor (ODF),
sulfate optimization

ABSTRACT
This report briefly discusses the mechanism of sulfate attack and the role of selected
supplementary cementitious materials (SCMs) in reducing this attack in concrete. The
relationship between sulfate resistance and the chemical, physical, and mineralogical
composition of SCMs has been elucidated. Based on a number of bench scale studies several
models predicting sulfate resistance in fly ash-containing concretes have been cited and
discussed. These include the derivations of 1) R factor related to active lime/iron oxide ratio,
whereby low R factor values (< 3.0) favor sulfate resistance, 2) calcium aluminate potential
factor (CAP) based on (lime + alumina + iron)/silica ratio and its direct relationship with
calculated sulfate equivalent (CSE) to predict sulfate resistance, and 3) oxide durability factor
(ODF) as a function of (lime • free lime)/(silica + alumina + iron) ratio, wherein a decrease in
ODF corresponds to an increase in sulfate resistance.
Although low C3A cement (Type V) is preferred in producing sulfate resistant concrete,
replacing cement with ground granulated blast furnace slag (GGBFS) in large amounts
(> 50%) has shown good sulfate resistance even with medium C3A cements. Similarly, the use of
7% silica fume with Type I cement also exhibited improved sulfate resistance compared with
plain Type I cement.
The report also discusses sulfate resistance of concrete that contained SCMs interground
and optimized at the cement plant as compared to mixed at the concrete batch plant. From the
very limited data available on the subject, use of interground SCMs with clinker has shown
improved sulfate resistance for concrete, primarily attributed to finer and better particle size
distribution that enhances the reactivity and reduces the permeability in concrete. The report also
cites that the optimization of sulfate should be based on 3-day strength instead of 1-day strength
as referred to by ASTM C 563. This may require a higher sulfate addition that can potentially
improve sulfate resistance, as the porosity of the system would markedly reduce.

REFERENCE
Bhatty, Javed I. and Taylor, Peter C., Sulfate Resistance of Concrete Using Blended Cements or
Supplementary Cementitious Materials, R&D Serial No. 2916a, Portland Cement Association,
Skokie, Illinois, USA, 2006, 21 pages.

1
 Sulfate Resistance of Concrete Using
Blended Cements or Supplementary
Cementitious Materials
By Javed I. Bhatty and Peter C. Taylor*

BACKGROUND
The degradation of cementitious materials due to sulfate attack has been recognized since before
the advent of portland cement (Bellport 1993). In the mid-18th century, Smeaton of Great Britain
worked on the development of improved mortars for the construction of Eddystone Lighthouse.
In the late 19th and early 20th centuries, Candlot (1890), Le Chatelier (1905), and Michaelis
(1909) studied sulfate attack on concretes containing portland cement. In North America, sulfate
attack on concrete was investigated in the early 20th century, notably by Bates, et al. (1913).
Since then, extensive studies have been made to identify the cause and develop methods to
prevent sulfate attack in concrete.
For new concrete infrastructures to be durable, guidelines on material selection, testing,
and construction practice need to be developed (Ahn 2005). In order for a concrete to be resistant
to sulfate attack in severe environments, cement with low C3A should be used in mixtures with
low permeability. The literature has also shown that low permeability concrete can be produced
by using supplementary cementitious materials (SCMs) such as fly ash, blast furnace slag, silica
fume, metakaolin, or other natural pozzolans. This report discusses the mitigation effect on
sulfate attack when concrete is produced with added SCMs.
Also discussed in this report is the effect on sulfate resistance of concrete using blended
cements containing SCMs through intergrinding, versus addition at the concrete batch plant. The
perception is that, because of sulfate optimization at the cement plant, concretes containing such
cements are more resistant to sulfate attack than concrete batch plant additions. Furthermore,
cements interground with SCMs may exhibit a better particle size distribution for enhancing
reactivity and reducing permeability in concrete compared to those produced by blending at the
concrete batch plant.

SULFATE ATTACK
Sulfates may be present in groundwater, and are often of natural origin, but can also come from
fertilizers and industrial effluents (Neville 1997). Attack on concrete by such materials is a
culmination of a series of reactions that occur in the presence of sulfate ions. Sulfate attack
manifests itself in the form of loss in strength, expansion, surface spalling, mass loss, and
eventually disintegration (Taylor 1997, Tikalsky and Carrasquillo 1989).

*
Senior Scientist jbhattey@ctlgroup.com and Principal Engineer/Group Manager ptaylor@ctlgroup.com,
CTLGroup, 5400 Old Orchard Road, Skokie, Illinois, USA, 847-965-7500.

2
MECHANISM OF SULFATE ATTACK
Sulfate attack is often discussed in terms of reactions between solid hydration products in
hardened cement paste (such as calcium hydroxide, Ca(OH)2, and calcium aluminate hydrate,
4CaO·Al2O3·13H2O) and dissolved compounds such as sodium sulfate (Na2SO4), magnesium
sulfate (MgSO4), and calcium sulfate (CaSO4). Their reactions with the solid phases in hardened
cement paste are as follows:

Sodium Sulfate (Na2SO4)

Sodium sulfate solution reacts with calcium hydroxide to form gypsum and Na(OH):
Na2SO4 + Ca(OH)2 + 2 H2O → CaSO4·2H2O + 2 Na(OH)

Sodium sulfate also reacts with calcium aluminate hydrate (4CaO·Al2O3·13H2O) and results in
the formation of ettringite:
6 Na2SO4 + 3 (4CaO·Al2O3·13H2O) + 34 H2O →
2 (3CaO·Al2O3·3CaSO4·32H2O) + 12 NaOH +2 Al(OH)3

Calcium Sulfate (CaSO4)

In aqueous conditions, calcium sulfate reacts with calcium aluminate hydrate

(4CaO·Al2O3·13H2O) to form ettringite (Bensted 1983):
3 CaSO4 + 4CaO·Al2O3·13H2O + 20 H2O → 3CaO·Al2O3·3CaSO4·32H2O + Ca(OH)2

When the supply of calcium sulfate becomes insufficient to form additional ettringite, calcium
aluminate hydrate (4CaO·Al2O3·13H2O) reacts with ettringite already produced to form
monosulfate (Bensted 1983):
3CaO·Al2O3·3CaSO4·32H2O + 2 (4CaO·Al2O3·13H2O) →
3 (3CaO·Al2O3·CaSO4·12H2O) + 2 Ca(OH)2 + 20 H2O

Magnesium Sulfate (MgSO4)

Magnesium sulfate attacks calcium silicate hydrate and Ca(OH)2 to form gypsum:
MgSO4 + Ca(OH)2 + 2 H2O → CaSO4·2H2O + Mg(OH)2

3 MgSO4 + 3CaO·2SiO2·3H2O → 3 CaSO4·2H2O + 3 Mg(OH)2 + 2 SiO2·H2O

Magnesium sulfate also reacts with calcium aluminate hydrate to form ettringite:
3 MgSO4 + 4CaO·Al2O3·13H2O + 2 Ca(OH)2 + 20 H2O →
3CaO·Al2O3·3CaSO4·32H2O + 3 Mg(OH)2

These reactions (to form gypsum and ettringite) are expansive in nature; therefore they
exert internal pressure in hardened concrete and eventually cause deterioration. It may also be
noted that the severity of sulfate attack depends on the concentration of sulfate solution, and the

3
rate at which the sulfate ions are replenished. If the concrete is exposed to sulfate bearing water
that is flowing rather than stagnant, it will undergo a higher rate of attack.

MITIGATION OF SULFATE ATTACK

Both calcium hydroxide (CaO·H2O or most commonly Ca(OH)2) and calcium aluminate hydrate
(4CaO·Al2O3·13H2O) involved in sulfate reaction are the major hydration products in cement
hydration. Calcium hydroxide forms as a result of C3S and C2S hydration∗, and calcium
aluminate hydrate is the principal product of C3A hydration. Therefore, any approach that
prevents the formation of Ca(OH)2 and 4CaO·Al2O3·13H2O should improve resistance to sulfate
attack.
As described by Neville (1997), three approaches to mitigate sulfate attack are usually
recommended. One is to use cement with low C3A content, the source of calcium aluminate
hydrates. ASTM C 150 addresses the need for sulfate resistance in cement by limiting C3A
content. Another is to reduce the Ca(OH)2 in the hydrated cement paste by using cements that
contain SCMs. The role of SCMs is to consume Ca(OH)2 in the pozzolanic reaction and to dilute
the C3A content of the system. SCMs with low lime contents also help mitigate sulfate attack by
reducing the alumina content of the mixture. In addition, concrete be made as dense as possible
in order to prevent the ingress of sulfate solutions. A combination of SCMs and low water-
cementitious materials ratio (to reduce permeability) is regarded as the most useful means of
increasing resistance to sulfate attack.

EFFECTS OF SCMs
The positive effects of SCMs on the resistance of concrete to sulfate are reflected in the
requirements of ACI 201, “Guide to Durable Concrete.” The use of fly ash and blast furnace slag
in making sulfate-resisting concrete has frequently been reported. Slag and other SCMs with low
lime contents reportedly mitigate sulfate attack by reducing alumina levels in the mixture.
Conversely, a high lime Class C fly ash may decrease sulfate resistance (Mather 1981, Tikalsky
and Carrasquillo 1992). However, the sulfate resistance of mixtures containing SCMs is
dependent upon the degree to which concrete is cured, as these materials may hydrate more
slowly and require extended curing to achieve sufficient impermeability. The majority of
concrete placed in the United States now contains at least one SCM. Ternary concrete mixtures
are often used to produce high performance concrete. Many SCMs result in greater later-age
strength and lower permeability, and consequently, improve durability and resistance to sulfate
attack.
Ahn (2005) has identified “permeability reduction” as a major parameter for controlling
sulfate attack in concrete. This parameter may be achieved by:
1) Reducing the water-cementitious materials ratio
2) Selecting proper material and mix proportions
3) Replacing cement with mineral admixtures (SCMs)
4) Adequately consolidating concrete
5) Providing adequate curing
∗
C3S, C2S, C3A and C4AF are cement chemists' notation rather than the oxide notation used up to this point.
Accordingly C=CaO, S=SiO2, A=Al2O3, F=Fe2O3; S¯ =SO3, and H=H2O. Also Ca(OH)2 or CaO·H2O in this
paragraph could be CH for consistency.

4
FLY ASH
The role of fly ash in controlling sulfate attack in concrete has been widely examined. Of the
chemical components, silica, lime, alumina, and iron oxide are considered the most critical. The
effectiveness of different fly ashes may vary significantly because of the large variation in these
compounds from source to source. Generally, low lime fly ashes show improved sulfate
resistance because they consume the available Ca(OH)2 in the hydrated cement paste, while lime
rich materials can hydrate independently and produce their own Ca(OH)2, thus increasing
exposure to sulfate attack. In addition, low lime materials form proportionally more C-S-H than
high lime materials, thus increasing the strength and reducing permeability, and increasing
sulfate resistance.
Tikalsky and Carrasquillo (1989) referred to noteworthy studies by Dikeou (1970),
Dunstan (1976, 1980, 1984, 1987), Kalousek (1972, 1976), Rosner (1982), Hartmann and
Mangotich (1987), Mehta (1986), and Manz et al. (1987).
As a result of a 27-year-long study on the sulfate resistance of concrete containing fly
ash, Dikeou (1970) concluded that fly ashes improved sulfate resistance of concrete regardless of
fly ash type or the cement used. Generally, the degree of resistance to sulfate was in the
following order (greatest to least), based on the cementitious material used:
Type V Cement + Fly Ash
Type II Cement + Fly Ash
Type V Cement
Type II Cement
Type I Cement + Fly Ash
Type I Cement

According to Dunstan (1976, 1980, 1984, 1987), concretes containing low-calcium fly
ash are more resistant to sulfate attack than those containing high-calcium fly ash or no fly ash.
Class C fly ashes produced from lignite or subbituminous coals typically contain calcium-rich
glass and crystalline gehlenite phases. Low-calcium fly ashes produced from anthracite or
bituminous coal are generally composed largely of mullite phases. Fly ashes having gehlenite-
like composition are reactive by nature, and hence are more prone to sulfate attack than mullite
containing fly ashes.
Based on his data, Dunstan (1976, 1980, 1984, 1987) proposed a method of predicting
sulfate resistance of concrete containing fly ash. The method computes factor R by using CaO
and Fe2O3 contents in the ash by the flowing equation:

CaO (%) − 5
R=
Fe2O3 (%)

Dunstan (1976) predicted the level of sulfate resistance for concrete containing fly ash by
the R factor as given in Table 1.

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 Table 1. Relationship Between R Factor and Sulfate Resistance

Limits of R Factor Sulfate Resistance

< 0.75 Greatly improved
0.75 to 1.5 Moderately improved
1.5 to 3.0 No significant change
> 3.0 Resistance reduced

However, Dunstan (1987) reported that the limit 3.0 for R was a subjective value proposed in
1980 from sulfate expansion data of 25% fly ash-containing concrete subjected to the 10%
sodium sulfate soak test. He suggested that a limit of 3.35 for R is more realistic and 3.70 may
even be acceptable. Concrete with higher R factor values will have reduced sulfate resistance,
whereas lower values will show improved sulfate resistance.
Rosner, et al. (1982) examined the usefulness of Dunstan’s R factor for four fly ashes
with R factors of 0.18, 0.29, 2.71, and 5.30. Based on the expansion data, three Class F ashes
with low R factors gave excellent sulfate resistance whereas Class C fly ash with R factor = 5.30
showed only marginal sulfate resistance when compared to the control cement. Contrary to
Dunstan’s prediction, two fly ashes with the highest R factors also performed adequately.
Mehta (1986), however, countered that Dunstan’s R factor prediction was flawed because
it did not take into account the crystalline form of reactive alumina in fly ash. Mehta’s studies
included several Class C fly ashes replacing 25% and 40% Type I cement having 11% C3A. The
data showed that despite having an R factor of 4.0, some ashes showed improved sulfate
resistance, whereas a number of ashes with R between 1.2 and 4.5 reduced the sulfate resistance.
Mehta (1986) concluded that sulfate resistance depends upon:
1) The stable hydrated aluminate phase when concrete is exposed to sulfate environments
2) The presence of calcium aluminosulfate or calcium aluminate hydrate makes concrete
susceptible to sulfate attack
3) The presence of reactive Al2O3/Fe2O3 is a true measure of aluminate reaction to sulfate
exposure

Manz et al. (1987) also concluded that with a given fly ash composition, R factor was
inadequate to predict sulfate resistance. Their data was based on a four-year study on fly ash
containing concretes with R factors ranging from 1.6 to 4.1, which showed minimal expansion
when exposed to sulfate environments. Manz et al. proposed revised prediction parameters based
on the reactive components in the fly ash. The first parameter is calcium aluminate potential
(CAP), which regards the glassy calcium, aluminate, and iron as detrimental to sulfate resistance,
and glassy silica as beneficial to sulfate resistance. CAP factor subtracts the inert crystalline
compounds and the crystalline compounds that do not take part in sulfate expansion reaction.
CAP is expressed as below:

CAP = (C* + A* + F*) / S*

Where,
C* = Bulk CaO – Reactive crystalline CaO (lime, anhydrite, C2S) –
inert crystalline CaO (melillite, merwinite)
A* = Bulk Al2O3 – inert Al2O3 (mullite)
F* = Bulk Fe2O3 – inert crystalline Al2O3 (hematite, spinel)
S* = Bulk SiO2 – inert crystalline SiO2 (quartz, mullite)

6
 The second parameter is a calculated sulfate equivalent (CSE). This factor assumes that S¯
(or SO3) in fly ash is desirable for forming early ettringite so that Ca(OH)2 in the cement paste is
reduced. CSE is expressed as follows:

CSE = Anhydrite + 1.7 S¯

The factor 1.7 accounts for the formation of additional anhydrite from other sulfate
sources in the fly ash. The proposed relationship between CAP and CSE in terms of sulfate
resistance of concrete is shown in Figure 1.
In another study, Hartmann and Mangotich (1987) used Class C fly ashes to develop a
more reliable method than Dunstan’s R factor to predict sulfate resistance in concrete. They
pointed out the following limitations of the R factor approach:
1) It could not predict sulfate resistance of concrete containing cement alone
2) The factor did not account for high calcium fly ashes
3) The extent of sulfate resistance did not always match the R factor
Calcium Aluminate Potential, CAP

Unsatisfactory

Satisfactory

Calculated Sulfate Equivalent, CSE

Figure 1. Sulfate resistance based on CAP and CSE parameters (After Manz, et al. 1987).

Based on a two-year study on sulfate resistance of concrete containing fly ash and
making use of data from Dunstan’s earlier work, Hartmann and Mangotich (1987) developed a
new factor to predict sulfate resistance of concrete known as oxide durability factor (ODF):

ODF = C(%) • Free lime (%) / S(%) + A(%) + F(%)

Where,
C =
A =
S =
F =
Bulk CaO in fly ash and cement
Bulk Al2O3 in fly ash and cement
Bulk SiO2 in fly ash and cement
Bulk Fe2O3 in fly ash and cement

7
 The principle advantage of Hartmann and Mangotich’s (1987) approach over Dunstan’s
was that it accounted for both Al2O3 and SiO2 and recognized the importance of crystalline
components of the cementitious materials (fly ash + cement) in concrete. It was claimed that the
oxide durability factor (ODF) correlated well, not only with their own experimental data, but also
with those from Dunstan’s studies. Typically, if there is a decrease in the value of ODF because
of fly ash addition, there should be a corresponding increase in sulfate resistance of concrete.
Rasheeduzzafar, et al. (1990, 1994) also examined the resistance of Type I, Type V, and
Type I cement + 20% Class F fly ash blends when subjected to various sulfate exposures such as
Na2SO4 and MgSO4. They concluded that cement-fly ash blends performed better than Type I
cement when exposed to Na2SO4 solution, but their performance became inferior when exposed
to a combined Na2SO4–MgSO4 environment. They contended that the mechanism of sulfate
attack in Na2SO4–MgSO4 exposure is intense on all cements but more so on blended cements,
and the attack is predominantly controlled by the presence of magnesium.
Al-Dulaijan et al. (2003) concluded that use of fly ash with Type I cement improved
sulfate resistance. Their testing included mortars made with Type I, Type V (sulfate-resistant
cement), and blends with fly ash exposed to varying concentrations of sodium sulfate solutions.
The sulfate resistance was evaluated by visual determination of specimen deterioration, loss in
compressive strength, and a combination thereof.
Mortars made with Type I cement exhibited a significant level of physical deterioration,
whereas Type I + 20% fly ash blends did not show any deterioration; Type V mortars showed
only marginal deterioration (see Table 2). Increased strength reduction due to sulfate reduction
was noted with mortars made with Type I cement. Strength reduction with Type V and Type I +
fly ash was lowest. The strength reduction of mortars was calculated as the sulfate deterioration
factor (SDF) as defined earlier by Rasheeduzzafar et al. (1994) by the following equation:

SDF (%) = (A – B) / A
Where,
A = Average compressive strength (MPa) of mortar cured in water
B = Average compressive strength (MPa) of mortar cured in sulfate solution

Ground Granulated Blast Furnace Slag (GGBFS)

Studies have shown that ground granulated blast furnace slag (GGBFS) also improves the sulfate
resistance of concrete. GGBFS is glassy in nature and thus reacts with Ca(OH)2 in hydrated
cement paste. Higher levels of cement replacement by slag (over 60%) appear to be more
effective as, according to Wong and Poole (1988), the consumption of Ca(OH)2 becomes more
pronounced.
The use of GGBFS in producing sulfate-resistant concrete has been recognized by both
ACI (1991) and ASTM (1997), who reported blended cements with 60% to 65% slag as widely
used in sulfate- and sea-water-resistant concretes.
Hogen and Meusel (1981) evaluated the use of slag in producing sulfate-resistant
concrete. They used Type I/II, II, and V cement blends with slag at 40%, 50%, and 65% cement
replacement. The sulfate resistance was significantly improved with Type II cement and to a
lesser degree with Type I/II and V cements. The improvement increased with increasing slag

8
addition. Also, the most improvement in sulfate resistance was recorded with Type II cement
containing 6.3% C3A compared to Type I/II and Type V cements that contained 6.3% and 3.7%
C3A respectively. In a separate study, Guyot et al. (1983) also confirmed that using cement with
more than 70% slag imparted effective sulfate resistance to concrete. It was also noted that 15%
to 20% addition of slag also provided protection from sulfate attack, provided the C3A contents
of the cement were low.
Fearson (1986) examined a series of slag-blended cement mortars exposed to sodium
sulfate environments. The slag contents ranged from 30% to 70% and the water-cementitious
materials ratio varied between 0.45 and 0.60. It was noted that mortars made with 70% slag were
superior to the sulfate resistant portland cements when specimens were compared at the same
water-cementitious materials ratio. At 50% slag replacement, the mortars were similar to, or in
certain cases better than, the sulfate resistant cements. Even 30% replacement of slag imparted
some degree of sulfate resistance, though inferior to that of typical sulfate resistant cements.
Selected specimens using 80% slag were tested at water-cementitious materials ratio = 0.60, and
were found to be highly sulfate resistant.
Osborne (1991) studied several blends of cements with granulated and pelletized slags
with respect to sulfate resistance and compressive strength development in concrete. The relative
effects of Al2O3 in slag and C3A in cements were also investigated. It was noted that a 70%
replacement by slag having low/medium Al2O3 (7.5% to 11.5%) in cement with medium C3A
(9%) produced concrete with good sulfate resistant properties. In similar studies, Fearson and
Higgins (1992) tested two slags with 11.5% and 15.5% Al2O3, respectively, and their composite
with 13% total Al2O3. The slags were blended with a cement of 10.2% C3A. The tests showed
that at a water-cement ratio of 0.60, a 70% replacement by all slags and 50% replacement by the
composite slag produced sulfate resistant concretes. At a water-cement ratio of 0.45, all slags at
70% and 50% replacement, as well as 30% replacement with composite slag, produced sulfate
resistant concretes.
Hemmings et al. (1995) tested North American sources of GGBF slags and confirmed
their effectiveness in reducing sulfate related expansion of concrete. It was confirmed that with
50% GGBF addition to Type 10 cements (having medium to high C3A contents), sulfate
expansion could be significantly reduced. In comparison, the beneficial effects were at least
similar to or better than a Type 50 sulfate resistant cement. The one-year expansion data for
concrete specimens made with Type 10, Type 50 sulfate resistant cements, and the cement-slag
blends are shown in Figure 2. It is noteworthy that the expansion plots for cement-slag blends are
well below those for Type 10 and Type 50 cements.

9
 0.6
High C3A Type 10 cement
0.5

Ex 0.4
pa Medium C3A Type 10 cement
nsi
on, 0.3
%
0.2
Low C3A sulfate
resistant
0.1 50:50
Cement
slags
0
0 10 20 30 40 50 60
Age, weeks
Figure 2. Sulfate expansion data for mortars produced with sulfate resistant portland cements and
cement blends containing slag (Hemmings, et al. 1995).

Silica Fume
Al-Dulaijan et al. (2003) used silica fume to enhance sulfate resistance of blended cement
mortars. Again, the superior performance of the ternary system was attributed to:
1. The pozzolanic reaction by silica fume that consumes CH and forms secondary
C-S-H, thus increasing overall C-S-H formation and reducing permeability
2. The dilution of C3A content due to the overall reduction of cement in concrete

Among others, cements evaluated for sulfate resistance were: Type I, Type V, and Type I +
7% silica fume. Fifty-mm cube mortar specimens were made using a water-cementitious
materials ratio of 0.50. The mortars were subjected to sulfate exposures having varying
concentrations of sodium sulfate for two years. Compressive strength and physical deterioration
of mortars were observed to correlate with sulfate resistance.
The data suggested that both strength and deterioration was influenced by cement type,
sulfate concentration, and the exposure time. Overall, Type V cement exhibited good resistance,
in terms of low strength reduction and deterioration, followed by Type I + 7% silica fume, and
plain Type I cement. (A Type I + 20% fly ash performed best when tested under identical
conditions.) Selected data on specimen deterioration caused by sulfate exposure is given in
Table 2.

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 Table 2. Deterioration Rating of Mortar Specimens Caused by Sulfate Exposure

Cement Sulfate Deterioration rating in exposure time

type solution (%) 4 months 8 months 15 months 24 months
Type I
1 0 1 2 3
2 2 2 3 4
4 3 3 3 3
Type V
1 0 0 0 1
2 0 0 0 2
4 1 1 1 3
Type I + 7% silica fume
1 0 0 1 1
2 0 0 1 2
4 1 2 2 3
Type I + 20% fly ash
1 0 0 0 1
2 0 0 0 1
4 0 1 2 2
0 = no deterioration, 1, 2, 4 = increasing rate of deterioration

A ternary mix containing cement with fly ash and silica fume is relatively common in
Canada. For instance, CSA Type 10E-F/SF cement is one with equivalent strength performance
to Type 10 cement. This cement contains fly ash as the primary SCM and silica fume as the
secondary SCM.

Blending vs. Intergrinding

The subject of intergrinding SCMs with clinker as opposed to separate batching to produce
blended cements has been discussed only occasionally, although both processing and material
advantages have been noted with intergrinding.
An early work by Davis et al. (1937) reported intergrinding of fly ash and clinker in
producing cement blends. The mixtures were ground for the same length of time as required to
produce portland cement of a given fineness. The effect of intergrinding was to increase the
fineness of the blended cement. The interground cement containing 20% fly ash showed 8%
increase in 7-day compressive strength compared with the blended cement; the one-year strength
was identical however, suggesting that the effect of intergrinding was only beneficial at the early
ages.
U.S. Army Corps of Engineers (1960) also reported that intergrinding fly ash, clinker,
and gypsum could produce satisfactory blended cement. It was realized that the reactivity of
cements containing fly ash decreased with increasing fly ash content but increased with the
increasing fineness of fly ash. It was also reported that since the fly ash was harder to grind than
the clinker, and since the difference in relative grindabilities appeared to increase as the
percentage of fly ash decreased, it was economical to grind fly ash-blended cements in stages
rather than as a single operation.

11
 Pandey et al. (2003) also studied the effects of SCMs on cement performance after
intergrinding with clinker and gypsum. The materials tested were fly ash, limestone, calcined
clay, and microsilica (silica fume). Two sets of blends were prepared. The first set used blended
fly ash at 5% to 35% clinker replacement. The second set replaced between 5% and 25% of the
clinker, using ternary mixtures of fly ash, calcined clay, microsilica, and limestone that were
interground with the clinker in a laboratory ball mill. These blends were tested for strength and
durability. Although the fineness of blends with 35% fly ash was high, their early-age mortar
cube strength gain was lower than the plain cement; the strength gains at 90 days and beyond
were noticeably higher. The early-age loss in strength could well be due to the dilution factor,
while the strength gain at later ages could be a combination of particle fineness and the
pozzolanic reactivity of the fly ash. Similar trends were observed when the cubes were cured in
sulfated solutions. Pandey et al. (2003) reported that the presence of fly ash enhanced the
strength when compared to plain mortar cubes cured in sulfate solution under identical
conditions. The maximum gain in strength was noted with 25% fly ash, when mortars become
more impervious due to the formation of additional C-S-H and the ensuing refinement of pores.
Nielsen (1980) and Osbǽck (1981) observed energy and strength advantages when fly
ash was interground with clinker. Osbǽck (1981) also noted an increase in fineness, decrease in
porosity and air content, and subsequent increase in density and strength when intergrinding was
used to produce cements containing fly ash. The effect of intergrinding fly ash vs. separate
batching on the reduction of alkali-silica reactivity has also been reported by Farbiarz et al.
(1995). Their data showed that using interground blended cement with fly ash significantly
reduced the alkali-silica reactivity of concrete. The improved effectiveness can be attributed to
an increase in fineness of the fly ash particles, either by grinding the fly ash particles or by
deflocculating large fly ash agglomerations, or a combination of both. Although the mechanisms
of sulfate attack and deleterious expansion due to ASR are different, some similarities exist, such
as a dependence on permeability. Therefore, this improvement in ASR-resistance might parallel
an improvement in sulfate resistance.
Freeman and Carrasquillo (1995) studied the effect of intergrinding on sulfate resistance.
Two concrete mixtures were produced using Type II cements and 35% Class C fly ash: one in
which the fly ash was added at the time of batching and the other in which the fly ash was
interground with the cement. The concrete mixes were spiked with varying amounts of soluble
sodium sulfate added to the mix water, based on the hypothesis that increasing sulfate and alkali
levels may improve the sulfate resistance of concrete.
Comparatively, the blended cements that contained interground fly ash were more
resistant to sulfate attack. This effect is clearly evident with concrete samples using two fly ashes
(see Figures 3 and 4).

12
 2.5
No Na2SO4 # = Na 2O Equivalent

Sulfate Susceptibility Rating

6.8
1.0 Limit
2
Type II cement concrete
1.5

5.4
1
4.1
3.2
0.5
1.7 2.4

0
0 1 0.3 0.4 0.5 0.6 0.7 0.9 1.1
Sulfate/Aluminate Equivalent
Fly Ash as Admixture Fly Ash Interground

Figure 3. Sulfate susceptibility of concrete containing fly ash A added at batch plant compared
with interground (Freeman and Carrasquillo 1995).

2.5
No Na2SO4 # = Na2O Equivalent
Limit
Sulfate Susceptibility Rating

Admixture 0.9 1.2 6.2

2
Type II cement concrete
4.6
1.5

3.4
1

2.5
0.5
1.8

0
0 1 0.3 0.4 0.5 0.6 0.7 0.9 1.1

Sulfate/Aluminate Equivalent

Fly Ash as Admixture Fly Ash Interground

Figure 4. Sulfate susceptibility of concrete containing fly ash B added at batch plant compared
with interground (Freeman and Carrasquillo 1995).

Intergrinding fly ash may have improved the ability of particles to react with sodium
sulfate while the concrete was still fresh. The reactivity may also have improved due to a
changed particle size distribution and improved degree of dispersion. It was also evident that
optimum resistance to sulfate resistance was noted when the SO3 to C3A equivalent ratio of fly
ash-cement mix was between 0.5 and 0.6.
Another important parameter that favors an improvement in sulfate resistance is the
reported decrease in permeability of concrete when cements with interground fly ash are used
with or without soluble sodium sulfate in the mix water (Freeman and Carrasquillo 1995). After

13
two weeks of moist curing, the permeability of concrete made with interground fly ash cements
without sodium sulfate admixture was equal to or higher than that of the Type II cement.
However, after three months, the permeability of concrete containing cement with interground
fly ash was significantly lower than that of Type II cement. Figure 5 shows ASTM C 1202 data
for concrete containing interground fly ash cements. The addition of sodium sulfate admixture
(4% to 5%) significantly decreased the chloride penetration (loosely related to permeability) of
concrete after two weeks curing. However, after three months, the chloride penetration of
concrete containing interground fly ash only was comparable to those containing sodium sulfate
admixture.

12000
Fly Ash A no additive
Permeability, Coulombs

10000

8000 Type II cement

Fly Ash B no additive
6000

4000 Fly Ash A w ith additive

2000
Fly Ash B w ith additive
0
0 20 40 60 80 100
Moist Curing, Days

Figure 5. Chloride permeability of concrete containing interground fly ash cements with or without
sodium sulfate additive (Freeman and Carrasquillo 1995).

Sulfate Optimization
The ASTM C 563 sulfate optimization method describes how to adjust the SO3 level in cement
to maximize its compressive strength. This method employs 1-day strength for mortar cubes
made using 1:1 cement:sand proportions by mass. However, Hawkins (2002) has suggested that
the SO3 optimization should be determined on the basis of 3-day compressive strength instead of
1-day strength. Using data from several mortars made with varying additions of SO3 levels and
testing at 1, 3, and 7 days, Hawkins noted that optimum sulfate dosage increased with curing
time (Figure 6).

14
 5000

Compressive Strength, psi

Optimum 3.80% 1-Day
4000 3-Day
Optimum 3.40%
7-day

3000
Optimum 2.75%
2000

1000

0
0 1 2 3 4 5 6

Sulfate, %
Figure 6. Optimum sulfate as a function of curing time. (Hawkins 2002).

Hawkins (2002) demonstrated that SO3 optimization using 3-day strength not only
improved the strength but also the sulfate resistance by reducing porosity; it also reduced the
drying shrinkage. These properties are mostly attributed to the interaction of SO3 with aluminate
phases in cement, which results in early-age modification of cement paste microstructure and
affects expansion, shrinkage, and porosity of the system.
Hawkins (2002) emphasized the need to adopt a similar approach of SO3 optimization for
cements using SCMs. Typically, ground granulated blast furnace slag also contains large
proportions of alumina that reacts with SO3 to form ettringite and can directly interfere with the
sulfate optimization. Using cement-slag mixtures in concrete containing 30% and 50% slag by
mass and having Blaine finenesses of 430 m2/kg, 490 m2/kg, and 550 m2/kg, Hawkins (2002)
again noted that for optimum SO3 determination, 3-day strength data (instead of 1-day strength)
were more appropriate. Such optimization improved the compressive strength, drying shrinkage,
and sulfate resistance in concrete when compared with those made with nonoptimized cement-
slag mixtures. Mixtures prepared by using 3-day-optimum-sulfate contents with slag and having
varying Blaine finenesses are shown in Table 3. Values of 1-day-optimum-sulfate cements are
also shown for comparison.

Table 3: Test Data for Cements Prepared Using Different Optimization Ages and Slag Contents

30% Slag: Cement Mixture 50% Slag: Cement Mixture

2
Blaine, m /kg 430 490 550 430 490 550
3-day Optimum SO3, % 3.98 4.08 4.08 4.39 4.55 4.85
1-day Optimum SO3, % 2.79 3.06 3.10 3.02 3.15 3.15

Hawkins (2002) concluded that if SCMs are interground with clinkers during finish
milling, then optimization needs to be done on the interground cement. If SCMs are ground
alone, gypsum should be interground with them at the optimum level as a mass percentage.

15
SUMMARY
This report briefly discusses the mechanism of sulfate attack and ways to mitigate it in concrete.
The role of supplementary cementitious materials (SCMs) such as fly ash, silica fume, and
ground granulated blast furnace slag in reducing sulfate attack in concrete has been addressed.
The relationship between sulfate resistance and the chemical, physical, and mineralogical
composition of SCMs and their proportioning have also been elucidated. Based on the bench-
scale studies, computation of several factors for predicting sulfate resistance in concrete
containing fly ash are discussed as a function of fly ash-cement chemistry. They are:
• R factor based on active lime/iron oxide ratio. It was noted that low R factors (< 3.0)
favored sulfate resistance; therefore Class F fly ashes with low values of R factor gave
better sulfate resistance compared with Class C fly ashes having high values of R factors.
• Calcium aluminate potential factor (CAP) based on (lime + alumina + iron)/silica ratio
and its relation with calculated sulfate equivalent (CSE) to predict sulfate resistance. The
CAP/CSE ratios lying below the correlation line show satisfactory sulfate resistance.
• Oxide durability factor (ODF) based on (lime • free lime)/(silica + alumina + iron) ratio.
A decrease in ODF value corresponds to an increase in sulfate resistance.

Although the computation models are helpful in predicting sulfate attack based on the
composition of cement and SCMs present in the mix design, testing under field conditions is
required to evaluate their acceptability.
The report also discusses the use of granulated ground blast furnace slag (GGBFS) in
mitigating the sulfate attack. Although the use of low C3A cement (Type V) is generally
preferred for sulfate resistance, replacing cement with ground granulated blast furnace slag
(GGBFS) at larger amounts (> 50%) has shown good sulfate resistance even with cements of
medium C3A contents. Use of 7% silica fume with Type I cement also exhibited sulfate
resistance compared with plain Type I cement.
Also discussed in the report is the sulfate resistance of concrete produced by cements that
contained SCMs interground and optimized at the cement plant, versus mixing at the concrete
batch plant. Very limited data is available on the subject. However, interground SCMs with
clinker have shown improved sulfate resistance. This could be because the interground SCMs
acquire finer and better particle size distribution, which enhances the reactivity and reduces the
permeability of concrete. Optimization of the sulfate content of the cementitious system is also
likely to contribute to the improved performance.
The data also suggest that sulfate optimization of cement be based on 3-day strength
instead of 1-day strength as used by ASTM C 563. This may require a higher dose of sulfate
addition that can potentially reduce sulfate resistance, since the porosity of the system is
markedly reduced.

16
REFERENCES
ACI Manual of Concrete Practice 1991, Part 3, Use of Concrete in Buildings – Design,
Specifications, and Related Topics, 318R-28, American Concrete Institute, Detroit, Michigan,
USA, 1991.

Ahn, N., “Effects of C3A and Mineral Admixtures on the Sulfate Attack Using ASTM C 1012,”
Journal of ASTM International, Vol. 2, No. 2, Paper ID JAI12472, February 2005.

Al-Dulaijan, S.U.; Muslehuddin, M.; Al-Zahrani, M.M.; Sharif, A.M.; Shameem, M., and
Ibrahim, M., “Sulfate Resistance of Plain and Blended Cement Exposed to Varying
Concentrations of Sodium Sulfate,” Cement & Concrete Composite, Vol. 25, pages 429 to 437,
2003.

ASTM C 989-04 “Specification for Ground Granulated Blast-Furnace Slag for Use in Concrete
and Mortars,” Vol. 04.02, ASTM International, Philadelphia, Pennsylvania, USA, 2004.

Bates, P.H.; Phillips, A.J., and Wig, R.J., Action of the Salts Water and Sea Water on Cements,
Paper #12, US Department of Commerce, National Bureau of Standards and Technology, 1913.

Bellport, B.P., “Combating Sulfate Attack on Concrete on Bureau of Reclamation Projects,”

Chapter 5 in Performance of Concrete, Ed. Swenson, 1993.

Bensted, J., “Hydration of Portland Cement,” Advances in Cement Technology, Ed. S. N. Ghosh,
Pergamon Press, Oxford, England, pages 307 to 347, 1983.

Candlot, E., Bull. Soc. Encour. Ind. Natn., 682, France, 1890.

Davis, Ramond E.; Carlston, Roy W.; Kelly, J.W., and Davis, Homer E., “Properties of Cement
and Concretes Containing Fly Ash,” Journal ACI, Proceedings, Vol. 33, pages 577 to 612, 1937.

Dikeou, J.T., Fly Ash Increase Resistance of Concrete to Sulfate Attack, Research Report No. 23,
United States Department of the Interior, Bureau of Reclamation, 17 pages, 1970.

Dunstan, E.R., Jr., Performance of Lignite and Subbitumenous Fly Ash in Concrete – A
Progress Report, United States Bureau of Reclamation Report REC-ERC-76-1, January 1976.

Dunstan, E.R., Jr., “A Possible Method of Identifying Fly Ashes that will Improve Sulfate
Resistance in Concrete,” Cement, Concrete and Aggregates, CCAGDP, Vol. 2, No. 1, pages 20
to 30, 1980.

Dunstan, E.R., Jr., Fly Ash and Fly Ash Concrete, United States Bureau of Reclamation Report
REC-ERC-82-1, May 1984.

17
Dunstan, E.R., Jr., “Sulfate Resistance of Fly Ash Concrete – The R-Value,” Bryant and
Katherine Mather Symposium on Concrete Durability, SP100, American Concrete Institute,
pages 2027 to 2040, 1987.

Farbiarz, J.; Carrasquillo, R.L.; and Snow, P.G., “Effect of Intergrinding Versus Separate
Batching of Fly Ash on Alkali-Aggregate Reaction in Concrete,” in 37th IEEE Technical
Conference, XXXVII Conference Record, San Juan, Puerto Rico, pages 179 to 196, 1995.

Fearson, J.P.H., “Sulfate Resistance of Combinations of Portland Cement and Ground

Granulated Blast Furnace Slag,” SP91-74, Madrid, American Concrete Institute, pages 1495 to
1524, 1986.

Fearson J.P.H., and Higgins, D.D., “Sulfate Resistance of Mortars Containing Ground
Granulated Blast Furnace Slag with Variable Alumina Content,” SP132-82, Istanbul, American
Concrete Institute, pages 1105 to 1132, 1992.

Freeman, R.B., and Carrasquillo, R.L., “Production of Sulfate-Resistant Concrete Containing

High-Calcium Fly Ash and Sodium Sulfate Admixture,” Fly Ash, Silica Fume, Slag, and Natural
Pozzolans in Concrete, Proc. 5th CANMET/ACI Int. Conf., pages 153 to 176, Milwaukee,
Wisconsin, USA, 1995.

Guyot, R.; Ranic, R., and Varizat, A., “Comparison of the Resistance to Sulfate Solutions and to
Sea Water of Different Portland Cements With or Without Secondary Constituents,” ACI SP79-
24, Proc. CANMET/1st Int. Conf. on Use of Fly Ash, Silica Fume, Slag, and Other Mineral By-
Products in Concrete, Montebello, Quebec, Canada, pages 453 to 469, 1983.

Hartmann, C., and Mangotich, E., “A Method of Predicting Sulfate Durability of Concrete,”
presented at Bryant and Katherine Mather Symposium on Concrete Durability, SP 100,
American Concrete Institute, 1987.

Hawkins, P., SO3 Optimization for Ground Granulated Blast Furnace Slag, Bulk Materials
International Slag Symposium, Hershey, Pennsylvania, May 2002.

Hemmings, R.T.; Cornelius, B.J.; Mikols, W.J., and Luther, M.D., “New North American
Sources of Ground Granulated Blast Furnace Slag for Improving the Sulfate Resistance of
Concrete,” Proc. 5th CANMET/ACI Int. Conf. Fly Ash, Silica Fume, Slag, and Natural Pozzolans
in Concrete, Supplementary Papers, pages 595 to 610, Milwaukee, Wisconsin, USA, 1995.

Hogen, F.J. and Meusel, J.W., “Evaluation of Durability and Strength Development of Ground
Granulated Blast Furnace Slag,” Cement, Concrete, and Aggregates, CCAGDP, Vol. 3, No. 1,
pages 40 to 52, Summer 1981.

Kalousek, G.L.; Porter, L.C., and Benton, E.G., “Concrete in Long-Term Service in Sulfate
Environments,” Cement and Concrete Research, Vol. 2, pages 79 to 89, 1972.

18
Kalousek, G.L.; Porter, L.C., and Harboe, E.M., “Past, Present, and Potential Developments of
Sulfate-Resistance Concretes,” Journal of Testing and Evaluation, JTEVA, Vol. 5, No. 6, pages
347 to 354, Sept. 1976.

Le Chatelier, “Experimental Researches on the Constitution of Hydraulic Mortars,” translated by

Mack, J.L., McGraw, New York, New York, USA, 1905.

Manz, O.E.; McCarthy, G.J.; Dockter, B.A.; Johnson, D.M.; Swanson, K.D., and Stienwand,
S.J., “Sulfate Resistance of Lignite and Subbitumenous Fly Ash Concrete: Tests Results and
Proposal for an Improved R-Factor,” presented at Bryant and Katherine Mather Symposium on
Concrete Durability, Atlanta, Georgia, USA, 1987.

Mather, K., “Factors Affecting Sulfate Resistance in Mortars,” Proceedings of the 7th
International Congress on the Chemistry of Cement, Paris, Vol. IV, pages 580 to 585, 1981.

Mehta, P.K., “Effect of Fly Ash Composition on Sulfate Resistance of Cement,” ACI Journal,
Vol. 83, No. 6, pages 994 to 1000, Nov.-Dec. 1986.

Michaelis, W., Sr., “The Hardening of Cement under Water,” Cement Engineering News,
translated by Michaelis, W., Jr., and published by Cement and Engineering News, Chicago,
Illinois, USA, 1909.

Nielson, A.H.C., “Preparation of Fly Ash Cements,” Proceedings of the 7th International
Congress on the Chemistry of Cement, Paris, Vol. III, pages IV-72 to IV-77, 1980.

Neville, A.M., Properties of Concrete, 4th. ed. John Wiley & Sons, Inc., New York, New York,
USA, 1997.

Osbǽck, B., “Effects of Grinding on Properties of Fly Ash Cements,” in Effects of Fly Ash
Incorporation in Cement and Concrete, Proc. Symposium N, Ed. S. Diamond, Materials
Research Society, University Park, Pennsylvania, USA, pages 280 to 288, 1981.

Osborne, G.J., “The Sulfate Resistance of Portland Cements and Blast Furnace Slag Cement
Concretes,” Proceedings of the 2nd CANMET/ACI Int. Conf. on Durability of Concrete, ACI
SP126-56, pages 1047 to 1070, Montreal, Canada, 1991.

Pandey, S.P.; Singh, A.K.; Sharma, R.L., and Tiwari, A.K., “Studies on High-Performance
Blended/Multiblended Cements and Their Durability Characteristics,” Cement and Concrete
Research, Vol. 33, pages 1433 to 1436, 2003.

Rasheeduzzafar; Dhakhil, F.H.; Al-Gahtani, A.S; Al-Saadoum, S.S., and Bader, M.A.,
“Influence of Cement Composition on the Corrosion of Reinforcement and Sulfate Resistance of
Concrete,” ACI Material Journal, Vol. 87, No. 2, pages 114 to 122, 1990.

19
Rasheeduzzafar; Al-Amoudi, O.S.B.; Abduljauwad, S.N., and Muslehuddin, M., “Magnesium-
Sodium Sulfate Attack in Plain and Blended Cements,” Journal of Materials in Civil
Engineering, Vol. 6, No. 2, pages 201 to 222, May 1994.

Rosner, J.C.; Chehovits, J.G., and Warburton, R.G., “Sulfate Resistance of Mortars Using Fly
Ash as Partial Replacement for Portland Cement,” Proceedings 6th International Ash Utilization
Symposium, Reno, Nevada, USA, 1982.

U.S. Army Corps of Engineers, Portland-Pozzolan Cement Made with Tennessee Valley
Authority Fly Ash, Technical Report No. 6-541, 33 pages, U.S. Army Engineers Waterways
Experiment Station, Vicksburg, Mississippi, USA, May 1960.

Taylor, H.F.W., Cement Chemistry, 2nd. Ed., Thomas Telfold Publishing, London, 1997.

Tikalsky, P.J., and Carrasquillo, R.L., The Effects of Fly Ash on the Sulfate Resistance of
Concrete, Research Report #481-5, Center for Transport Research, The University of Texas at
Austin, Austin, Texas, USA, 317 pages, August 1989.

Tikalsky, P.J., and Carrasquillo, R.L, “Influence of Fly Ash on the Sulfate Resistance of
Concrete,” ACI Materials Journal, Vol. 89, No. 1, pages 69 to 75, 1992.

Wong, G.S, and Poole, T., Sulfate Resistance of Mortars Using Portland Cement and Blends of
Portland Cement and Pozzolan or Slag, Technical Report SL-88-34, US Army Corps of
Engineers, Washington, DC, 1988.

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