Construction and Building Materials 78 (2015) 85–91

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Construction and Building Materials

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Effects of class F fly ash on sulfate resistance of Type V Portland cement

concretes under continuous and interrupted sulfate exposures
Nader Ghafoori, Meysam Najimi ⇑, Hamidou Diawara, Mohammad S. Islam
Department of Civil and Environmental Engineering and Construction, University of Nevada Las Vegas, Las Vegas, NV, USA

h i g h l i g h t s

 Sulfate resistance of Type V Portland cement.

 Influence of fly ash on sulfate resistance of Type V Portland cement.
 Comparative influence of continuous and cyclic wet–dry exposures on sulfate resistance of concrete.

a r t i c l e i n f o a b s t r a c t

Article history: The current study evaluates influence of class F fly ash replacement level on the ettringite-based expan-
Received 28 July 2014 sion and gypsum formation (strength reduction and mass loss) of Type V Portland cement concretes. To
Received in revised form 3 December 2014 this aim, control concretes were made using Type V Portland cement with different contents of 333, 374
Accepted 2 January 2015
and 416 kg/m3. Fly ash contained concretes were designed by replacing 15, 20, 25 and 30% by weight of
Available online 16 January 2015
cement with fly ash. An experimental program was designed to monitor length change, mass loss, and
compressive strength reduction of mixtures under interrupted and continuously-immersed sulfate expo-
Keywords:
sure conditions. The results of this study revealed improvements in concretes’ resistance to sulfate attack
Type V Portland cement
Class F fly ash
by replacing a portion of cement with fly ash. The improvements, however, were not as much as expected
Sodium sulfate for class F fly ash. The optimum replacement level was different for different cement contents. It was
Expansion increased with increases in cementitious materials contents. No mass loss and strength reduction were
Exposure type observed within a year of exposure. The performances of mixtures under interrupted and continuous
Ettringite immersion were nearly similar. Both compressive strength and ettringite-based expansion of the studied
Gypsum specimens under interrupted sulfate immersion condition were marginally lower than those of continu-
Strength ously immersed specimens.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Concrete can deteriorate for several reasons and sulfate attack is
reported to be a major contributor to concrete premature failure. It
was reported that ‘‘concrete deterioration due to sulfate attack is
the second major durability problem, after reinforcement
corrosion’’ [1]. Sulfates can come from a variety of sources such
as groundwater, high clay-content soils, seawater, organic materi-
als in marshes, mining pits, and sewer pipes, and in different forms
including magnesium sulfate, sodium sulfate, calcium sulfate,
potassium sulfate, and ammonium sulfate [2]. Magnesium sulfate
is reported to be potentially more destructive than sodium sulfate,
and both are found to be more damaging than calcium, potassium,
and ammonium sulfates [3].
⇑ Corresponding author. Tel.: +1 7023470221.
E-mail address: najimim@unlv.nevada.edu (M. Najimi).
Sulfate attack can be either in the form of internal attack, which
is the result of chemical reactions between constituents of cement
paste and sulfate ions; or external attack, which mostly manifests
itself in the form of surface scaling similar in appearance to that of
freezing and thawing damage [3,4]. The chemical sodium sulfate
attack, which is the focus of this study, can have adverse effects
on concrete in two distinct forms: (1) expansion of cement matrix
generally attributed to the formation of ettringite compounds, and
(2) progressive loss of strength and mass due to deterioration of
hardened cement paste by gypsum formation [5].
There are a number of factors affecting the severity of sulfate
attack and resistance of concrete. These factors include parameters
related to: (1) concrete mixture ingredients and proportion such as
cement type, cement content, water-to-binder ratio, admixtures,
and supplementary cementitious materials, (2) curing and
hardened concrete properties such as curing condition, pore
structure, permeability, diffusivity, and mechanical properties,

http://dx.doi.org/10.1016/j.conbuildmat.2015.01.004
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
86 N. Ghafoori et al. / Construction and Building Materials 78 (2015) 85–91

and (3) exposure condition including sulfate type and concentra- the cementitious material reacts with sulfate ions to form gypsum
tion, immersion type, and exposure temperature [6]. While the [3]. The reaction with sodium sulfate is shown below:
first two groups are related to the concrete properties, the third
group is dealing with the application of concrete structures.
Na2 SO4 þ CaðOHÞ2 þ 2H2 O ! CaSO4  2H2 O ðGypsumÞ þ 2NaOH
Environmental conditions have a great influence on severity of sul- ð1Þ
fate attack. Sulfate concentration may fluctuate seasonally as a
Expansion due to sulfate attack is a three-step process. First,
localized migration of soluble salts due to weather changes [7].
ettringite forms in the cement matrix from the result of reactions
During the dry cycle sulfate can accumulate at the concrete
between the tricalcium aluminate in the Portland cement and sul-
surface, increasing in concentration and potential for causing dete-
fate ions from internal or external sources or both. More specifi-
rioration [8].
cally, calcium sulfate dihydrate (gypsum) combines with C3A to
Sulfate attack is particular a big problem in arid areas, where
form 6-calcium aluminate trisulfate hydrate (ettringite) [2]. The
the soil has high soluble salt content [7]. The water sprinkling dur-
reaction is as follows:
ing the long dry season and the rare rains during the spring season
expose the concrete floors and other concrete structures in contact 3CaO  Al2 O3 þ 3ðCaSO4  2H2 OÞ þ 26H2 O
with ground to a severe wet–dry sulfate condition. Such condition
! 3CaO  Al2 O3  3CaSO4  32H2 O ð2Þ
has been especially seen in the western region of U.S. In this region,
soil is sulfate rich and sulfate attack is harsh. Due to severity of pre-
mature failures, use of Type V Portland cement or sulfate-resistant
or : C3 A ðtricalcium aluminateÞ þ Gypsum þ 26H2 O
cement has been become mandatory in this region. Type V Port- ! Ettringite ðC6 AS3 H32 Þ
land cement contains limited amounts of C3A and C4AF which
Next, monosulfoaluminate is formed. Specifically, sulfate ions
are the main cement ingredients participating in the chemical sul-
from the ettringite react with the remaining C3A to form tetracal-
fate attack. Use of this type of cement, however, may not been a
cium aluminate monosulfate-12-hydrate (monosulfoaluminate).
complete solution for the above-mentioned problem. Different
The chemical reaction is given below:
agencies have been looking for a more permanent solution and
higher resistances to sulfate attack. 2ð3CaO  Al2 O3 Þ þ 3CaO  Al2 O3  3CaSO4  32H2 O þ 4H2 O
In pursuit of producing sulfate-resistant concrete, literature
! 3ð4CaO  Al2 O3  SO3  12H2 OÞ ð3Þ
studies have demonstrated that use of enough quantities of fly
ash, in particular low-calcium or class F fly ash, can effectively In the third step, ettringite is formed again when the monos-
increase resistance of concrete to chemical sulfate attack [1,9–15]. ulfoaluminate is brought into contact with a new source of sulfate
Dikeou [9] concluded that fly ashes improve sulfate resistance of ions. This reaction is shown below:
concrete regardless of fly ash type or the cement used. Al-Dulaijan
et al. [1] reached the conclusion that use of class F fly ash improves 4CaO  Al2 O3  SO3  12H2 O þ 2ðCaSO4  H2 OÞ þ 6H2 O
sulfate resistance of Type I Portland cement concrete. Torii et al. ! 3CaO  Al2 O3  3CaSO4  32H2 O ð4Þ
[10] showed excellent behavior of high class F fly ash content con-
cretes against chemical sulfate attack. Sumer [11] realized that The continued formation of ettringite compounds within
regardless of fly ash type, the addition of fly ash significantly confined solids causes significant internal pressure leading to
increases resistance of concrete to chemical sulfate attack. Dunstan expansion and cracking [2].
[12–15] concluded that concretes containing low-calcium fly ash
are more resistant to sulfate attack than those containing high-cal- 3. Experimental program
cium fly ash or no fly ash. While there are doubts on improving
3.1. Materials
resistance of concrete to sulfate attack by use of class C fly ash as
lime rich materials can hydrate independently, produce their own Type V Portland cement as mandated in the western regions of U.S, class F fly
calcium hydroxide and thus increasing exposure to sulfate attack, ash, and locally produced coarse and fine aggregates were used as the matrix con-
it is accepted that class F fly ash is quite effective in increasing sul- stituents. The physico-chemical properties of the used cement and fly ash are
reported in Table 1. As can be seen, the Type V Portland cement and class F fly
fate resistance of concrete. Class F fly ash consumes the available
ash complied with the requirements of ASTM C150 [16] and C618 [17], respectively.
amounts of calcium hydroxide making it unavailable to react with
sulfates. It is also quiet effective in reducing permeability of con- Table 1
cretes which improves chemical resistance by reducing the ionic Chemical and physical properties of cement and fly ash.
ingress, migration and concentration [11]. Optimum percentage
Chemical composition Type V Portland cement Fly ash
of fly ash replacement, however, should be considered to achieve
SiO2, % 20.6 58.9
suitable results.
Al2O3, % 3.7 20.5
This study was conducted to investigate how much class F fly Fe2O3, % 3.5 5.6
ash can be effective in improving resistance of Type V Portland MgO, % 3.9 –
cement concrete to the internal sulfate attack. Two sulfate expo- SO3, % 2.6 0.4
sure conditions of continuously immersed and interrupted cyclic CaO, % 63.7 7.5
Na2O eq., % 0.45 –
immersion were considered for this study to observe their effects
Loss on ignition, % 1.27 0.3
on the extent of chemical sulfate attack. Insoluble residue 0.23 –
Blaine, cm2/g 3880 –
2. Chemical processes of sulfate attack Specific gravity 3.15 2.33
Percent passing 45 lm, % 97.8 76.5
C3S, % 65.6 –
As discussed above, the chemical sodium sulfate attack happens C2S, % 9.5 –
in the forms of ettringite based expansion and/or gypsum forma- C3A, % 4.05 –
tion resulting in strength and mass losses. C4AF, % 10.5 –
Progressive loss of strength and mass occur when concrete is 3-Day compressive strength, MPa 26.4 –
7-Day compressive strength, MPa 33.2 –
exposed to external sources of highly concentrated sodium sulfate
28-Day compressive strength, MPa 42.9 –
(Na2SO4) or magnesium sulfate (MgSO4). Calcium hydroxide from
 N. Ghafoori et al. / Construction and Building Materials 78 (2015) 85–91 87

Table 2 3.3. Mixing, sampling, curing, and testing procedures

Aggregate properties.
An electric counter-current pan mixer with a capacity of 0.028 m3 was used to
Aggregate type Bulk SSD Absorption Dry rodded Fineness blend concrete components. The concrete mixtures (batch volume of 0.017 m3)
specific specific (%) unit weight modulus were used to cast 76  76  305 mm beams or 100  200 mm cylindrical speci-
gravity gravity (kg/m3) mens. The test specimens were moist-cured in a curing chamber for three days
Fine aggregates 2.77 2.79 0.9 – 3.01 (at 23 ± 1 °C) prior to exposure to a continuously or cyclic-immersed sodium sulfate
(0–4.75 mm) environment. Upon removal from the moist-curing room, each cylinder was
Coarse aggregates 2.76 2.77 0.4 1653 – weighed, and each prism was measured to determine its initial length. Half of the
(4.75–19 mm) specimens were continuously immersed in a 5% sodium sulfate solution, whereas
the remainders were placed in a cyclic sodium sulfate chamber. The fully immersed
condition was achieved by immersing the test specimens in an enclosed container
filled with a 5% sodium sulfate solution at the temperature of 23 ± 1 °C.
For the used cement, C3A and C4AF + 2C3A contents were 4.05% and 18.6%, respec- The interrupted cyclic immersion apparatus consisted of two tanks rigidly
tively, well below 5% and 25% limits of ASTM C150 [16]. The summation of pozzo- assembled and two pumps assemblies. The tanks were insulated boxes made of ply-
lanic oxides of the used fly ash, i.e. silica, alumina and iron oxide, was 85%, well wood and styrofoam to maintain a constant room temperature. The pump assembly
above minimum requirement of ASTM C618 [17]. Based on Eq. (5) suggested by was designed to run automatically every twelve hours and pump the sodium sulfate
Dunstan [13], the used fly ash has the ability to greatly improved sulfate resistance solution from the bottom tank to the top tank prior to the wet cycle (fully
of concrete. In Dunstan’s classification, fly ashes with R value of [more than 3], [1.5– immersed) and vice versa for the dry cycle (nonimmersed). The temperature for
3], [0.75–1.5], and [less than 0.75] can reduce sulfate resistance, result in no signif- both cycles was fairly uniform at 23 ± 1 °C.
icant change, moderately improve sulfate resistance, and greatly improve sulfate Each liter of the sodium sulfate solution initially contained 50 g of sodium sul-
resistance, respectively. R value for the used fly ash was 0.543, well below 0.75% fate and 900 ml of distilled water. Additional distilled water was added to raise the
for greatly improved resistance. It should be noted that there are a number of crit- volume to full one liter. The pH of the solution was measured before each use.
icisms in literature on Dunstan’s equation; in particular it was found that sulfate When the pH filled outside the range of 6.0–8.0, a new 5% sodium sulfate solution
resistance depended on the amount of reactive alumina and the presence of expan- was used. The volume of sulfate solution was kept constant at 3 times the volume of
sive phases in the fly ash and was not as strongly influenced by Fe2O3 as indicated the submerged specimens [19].
by the R factor. However, in absence of available data, this equation was used as the The interrupted immersion cycles were repeated every 12 h for a period of
only available source which could satisfy the potential of used fly ash in improving 360 days. At the ages of 180 and 360 days, the cylindrical concrete samples were
sulfate resistance of concrete. removed from the tank and tested in compression according to the ASTM C 39
[20]. To monitor length change, each prism was measured, in accordance with
the ASTM C 1012 [19], weekly for the first twelve weeks, bi-weekly for the next
CaO ð%Þ  5
R¼ ð5Þ 18 weeks and monthly thereafter until a year exposure was reached. The calcula-
Fe2 O3 ð%Þ
tion of the length change at any age was performed in accordance with the ASTM
The physical properties of fine and coarse aggregates are documented in Table 2. C 1012 [19].
A water-reducing admixture meeting requirements of ASTM C 494 [18] was also
used to keep the constant flow of 100 ± 6 mm for all the mixtures.

4. Results and analysis

3.2. Mixture proportions
Table 3 documents the mixture proportion of the studied concretes. Three dis-
tinct groups of concretes were investigated. These groups which named as group A,
B and C, had different cementitious materials contents of 333, 374 and 416 kg/m3,
respectively (corresponding to water-to-cementitious materials ratios of 0.50, 0.45
and 0.40). For each group, a control concrete was designed using sole Type V Port-
land cement as their binder. Fly ash contained concretes were then designed for
each group by replacing 15, 20, 25 and 30% by weight of cement with fly ash. Table 3
also reports the amount of used water reducing admixture. As seen, the demand for
water-reducing admixture decreased with increases in fly ash content, indicating
positive effect of fly ash on workability of concrete. Fly ash particles are small, hard
and round; hence, the workability of fresh concrete increased with their
application.
4.1. Bulk properties
4.1.1. Demolded unit weight
The one-day unit weights of the selected matrices, immediately
after demolding, are shown in Table 4. All concretes exhibited
demolded unit weights above the regular range for normal-weight
concrete (i.e. 2240–2400 kg/m3) [21], due to the relatively high
specific gravity of the coarse and fine aggregates (2.77 and 2.79,
respectively), as compared to that of most natural aggregates
(2.4–2.9) [21]. Additionally, owing to the lower specific gravity of
the fly ash (2.33) as compared to that of the Portland cement

Table 3
Mixture proportions.

Mixture identification Total Cma W/Cmb Fly ash/Cmc Type V cement Fly ash Fine aggregate Coarse aggregate WRAd
(kg/m3) (kg/m3) (kg/m3) (kg/m3) (kg/m3) (g/kg of Cm)
A. Control 333 0.50 0.00 333.0 0 881 1125 4.71
A. 15 0.15 283.0 50.0 875 1117 1.88
A. 20 0.20 266.4 66.6 873 1114 0.71
A. 25 0.25 249.7 83.3 871 1111 0.24
A. 30 0.30 233.0 100.0 869 1109 0.00
B. Control 374 0.45 0.00 374.0 0 823 1140 4.94
B. 15 0.15 317.9 56.1 816 1131 2.12
B. 20 0.20 299.2 74.8 814 1128 1.18
B. 25 0.25 280.5 93.5 812 1124 0.94
B. 30 0.30 261.8 112.2 810 1121 0.47
C. Control 416 0.40 0.00 416.0 0 753 1180 11.77
C. 15 0.15 353.6 62.4 744 1170 5.59
C. 20 0.20 332.8 83.2 743 1165 5.30
C. 25 0.25 312.0 104.0 741 1162 4.41
C. 30 0.30 291.2 124.8 738 1158 2.94
a
Cementitious materials.
b
Water-to-cementitious materials ratio.
c
Fly ash-to-cementitious material ratio (fly ash + cement).
d
Water reducing admixture.
88 N. Ghafoori et al. / Construction and Building Materials 78 (2015) 85–91

Table 4
Compressive strength results (MPa).

Mixture De-molded unit Continuous water-immersed Continuous sodium sulfate-immersed Cyclic sodium sulfate-immersed
identification weight (kg/m3)
Days
3 28 180 360 180 360 180 360
A. Control 2512 31.8 48.4 54.6 58.6 55.8 62.8 56.9 62.2
A. 15 2498 25.1 43.4 61.0 66.3 66.5 71.0 64.7 70.8
A. 20 2493 23.6 41.6 59.4 67.7 63.8 71.5 63.0 71.1
A. 25 2488 22.0 39.8 57.6 65.3 60.9 67.5 60.7 66.8
A. 30 2483 18.4 36.3 56.1 61.5 58.2 63.6 57.8 62.2
B. Control 2513 37.5 53.4 64.3 69.5 66.9 71.7 65.1 70.3
B. 15 2496 30.7 50.1 68.6 74.8 72.0 77.5 70.4 74.9
B. 20 2491 29.5 47.5 70.0 76.8 72.9 79.2 71.4 78.4
B. 25 2485 27.3 46.1 67.3 78.2 71.8 79.9 69.5 79.5
B. 30 2480 24.4 44.0 66.2 73.8 69.7 77.1 67.6 73.9
C. Control 2521 41.7 58.0 72.1 78.4 73.7 80.9 73.5 79.9
C. 15 2503 36.9 55.2 76.5 82.3 79.4 86.8 78.6 84.3
C. 20 2496 35.9 54.2 80.3 87.1 83.1 91.2 82.6 89.0
C. 25 2491 32.2 52.9 81.3 88.3 84.0 91.8 82.8 89.8
C. 30 2485 29.7 50.3 77.9 89.0 82.0 93.2 80.3 92.0

and 4.5% for group B mixtures and 5.5, 11.2, 12.7 and 10.8% for
group C mixtures. It was also observed that increases in total
cementitious materials contents led to higher optimum replace-
ment levels. The replacement levels of [15 and 20], [20 and 25]
and [25 and 30]% resulted in the highest improvements for group
A, B and C with total cementitious materials contents of 333, 374
and 416 kg/m3, respectively. This behavior may be attributed to
the depleted source of calcium hydroxide which limited the role
of the excess fly ash to merely fill the micro voids of concrete
matrix.

4.2. Ettringite-based expansion

The linear expansions of the studied mixtures under continuous

Fig. 1. Improvements in late-age compressive strength of fly ash contained
concrete when compared with compressive strength of control concrete.
(3.15), the fly ash contained concretes displayed slightly lower unit
weights when compared to those of the control concretes.
4.1.2. Compressive strength
Compressive strength of the studied mixtures was measured
after 3, 28, 180 and 360 days curing in standard saturated condi-
tion. The results are presented in Table 4 and Fig. 1. As can be seen,
fly ash contained concretes developed lower early age strength (3-
day and 28-day) than those of the control mixture. The 3-day com-
pressive strengths decreased by averagely 17.0, 20.3, 26.9 and
35.4% when 15, 20, 25 and 30% by weight of cement was replaced
with fly ash (average of all 3 groups). These reductions narrowed to
averagely 7.1, 10.5, 13.4 and 18.7% at the age of 28 days, respec-
tively. This finding was mainly due to the slow reactivity of the
Class F fly ash in early ages. The gains in compressive strength con-
tinued with increases in curing age and were more pronounced for
fly ash contained concrete after 28 days of curing. During these
periods, more calcium silicate hydrate (C–S–H) was produced in
fly ash contained concretes due to the reactions between fly ash
and Portland cement hydrated lime. Fig. 1 shows the improve-
ments in compressive strength at late age as average of improve-
ments in 180 and 360 days. For group A, late strengths (180 and
360 days) of mixtures having 15, 20, 25 and 30% fly ash were aver-
agely 12.4, 12.2, 8.5 and 3.8% higher than those of control concrete,
respectively. These enhancements were respectively 7.1, 9.6, 8.5
and interrupted cyclic immersions are presented in Table 5. Fig. 2
shows the ultimate expansion of mixtures after a year of exposure
under both immersion conditions. The discussion of the ettringite
formation as influenced by the immersion age, fly ash content,
and immersion type is presented below.
4.2.1. Influence of immersion age
Table 5 documents the level of expansion within age of immer-
sion. It can be observed that the highest rate of expansion of all the
tested matrices during the first 10–18 weeks of immersion, and
leveled off during the last 34 weeks of the immersion period. On
average, the studied mixtures (control and fly ash contained con-
cretes) reached 76% of their one-year expansion after only
10 weeks of continuous immersion. These expansions were 87%
and 95% of the one-year expansion, after 14 and 18 weeks of
immersion, respectively. Similarly, the studied mixtures reached
75, 87 and 95% of their one-year expansion after 10, 14 and
18 weeks of interrupted cyclic immersion, respectively.
These observations can be related to the availability of trical-
cium aluminates (C3A) and the degree of permeation of sulfate
with time. In the early stages of expansion, a greater amount of
C3A is available for the formation of ettringite reactions. As the
exposure age lengthens, less C3A is available for reaction and for-
mation of ettringite. Moreover, the already formed ettringite com-
pounds assist in reducing the rate of expansion by making it more
difficult for the sulfate solution to penetrate the cement matrix.
4.2.2. Influence of fly ash content
Fig. 2 shows the effects of fly ash replacement levels on ettring-
ite-based expansion. In order to highlight the results of Fig. 2, Fig. 3
 N. Ghafoori et al. / Construction and Building Materials 78 (2015) 85–91 89

Table 5
Linear expansion of the studied mixtures.

Mixture identification Linear expansion  104 (%)

Immersion age (weeks)
4 10 14 18 24 52
Continuously immersed condition
A. Control 30 46 52 56 58 60
A. 15 26 40 46 50 51 52
A. 20 28 42 48 52 53 55
A. 25 29 44 50 54 56 58
A. 30 32 48 54 58 60 62
B. Control 26 42 48 52 53 55
B. 15 22 37 43 46 47 49
B. 20 20 36 42 44 45 47
B. 25 23 39 45 49 50 51
B. 30 24 40 46 50 51 53
C. Control 22 38 44 48 49 50
C. 15 20 36 42 46 47 48
C. 20 18 33 39 43 44 45
C. 25 17 31 37 41 42 43
C. 30 19 34 40 44 45 46
Fig. 2. Ultimate expansion of mixtures after a year of immersion.
Interrupted cyclic condition
A. Control 28 44 50 54 56 57
A. 15 24 38 44 48 49 49
A. 20 26 40 46 50 51 52
A. 25 27 42 48 52 54 55
A. 30 30 46 52 56 58 59
B. Control 24 40 46 50 51 53
B. 15 20 36 42 45 46 48
B. 20 18 34 40 42 43 45
B. 25 21 37 43 47 48 49
B. 30 22 38 44 48 49 51
C. Control 20 36 42 46 47 48
C. 15 18 34 40 44 45 46
C. 20 16 31 37 41 42 43
C. 25 15 30 36 40 41 42
C. 30 17 32 38 42 43 44

Fig. 3. Improvements in ultimate expansion as a result of fly ash replacement.

presents the average improvements in ultimate expansion of

different fly ash contained concretes, when compared with ulti-
(a) The chemical effects:
mate expansion of the corresponding control concretes. Generally
- Consumption of free lime due to pozzolanic reaction of fly ash
speaking, replacing a portion of cement with fly ash was useful
and free lime (CaO), making it unavailable to react with the
in reducing expansion of the studied concretes. There were
sulfate,
different optimum replacement levels for different cementitious
- reduction in the amount of reactive aluminates available by
materials contents; which was increased by increases in cementi-
replacing cement, and
tious materials contents.
- formation of additional calcium silicate hydrates (C–S–H) due
For group A, made with a cementitious materials content of
to the pozzolanic reaction of fly ash with free lime, restraining
333 kg/m3, the ultimate expansions were 13.7, 8.5, and 3.4% lower
further expansion.
than that of control concrete for fly ash replacement levels of 15,
(b) The mechanical effect:
20, and 25%, respectively. On the other hand, ultimate expansion
- In a sodium sulfate environment, ettringite compounds were
of mixture A. 30 having 30% fly ash as cement replacement was
formed and acted as fillers for the spaces between concrete
3.4% higher than that of control concrete (A. Control). Replacing
particles, hence, reducing further sulfate penetration into the
15, 20, 25 and 30% by weight of cement with fly ash led to 10.2,
concrete.
14.8, 7.4 and 3.7% improvements in ettringite-based expansion of
group B concretes having cementitious materials content of
The drop in resistance to ettringite expansion beyond 15, 20
374 kg/m3. These improvements were respectively 4.1, 10.2, 13.3
and 25% replacement levels for cementitious materials contents
and 8.2% for group C concretes with cementitious materials con-
of 333, 374 and 416 kg/m3 may be attributed to the depleted
tent of 416 kg/m3. It can also be seen that for group A, 15% replace-
source of calcium hydroxide which limited the role of the excess
ment level showed the highest reduction in expansion. For group B,
fly ash to merely fill the micro voids of concrete matrix. A similar
the ettringite-base expansions decreased with increases in fly ash
trend observed in Fig. 1 for compressive strength development
content up to 20%, after which the ettringite-base expansions
corroborates with this explanation.
experienced gradual increases as the fly ash content increased to
25% and 30%. The pick of improvement was observed at 25%
replacement level for group C. The gain in resistance to ettringite 4.2.3. Comparison of immersion types
expansion of the fly ash concretes can be attributed to two factors The ettringite-based expansions were also compared for the
caused by the incorporation of fly ash in the matrix. two immersion types used in this investigation; namely,
90 N. Ghafoori et al. / Construction and Building Materials 78 (2015) 85–91
Fig. 4. 180-day compressive strength of the mixtures under standard curing
condition and sulfate immersion.
interrupted cyclic and continuous immersions. The test results
reported in Table 5 and Fig. 2 indicated that the studied concrete
mixtures exhibited marginally higher resistance to ettringite-
based expansion in the cyclic-immersed environment when
compared to continuously-immersed condition. After 10, 14, 18
and 52 weeks of interrupted cyclic exposure, the average linear
expansion of the studied concretes were lower by 5.0, 4.1, 3.8
and 4.2%, respectively, when compared to the continuously
immersed concretes.
On the whole, the used interrupted cyclic immersion did not
significantly affect the linear expansion of the test specimens
exposed to sodium sulfate environment. This may be mainly attrib-
uted to the conditions (i.e. temperature, relative humidity, etc.) of
the cyclic-immersed environment which were not severe enough
to cause a prejudicial internal relative humidity drop, a reduction
in permeability due to the formation of ettringite compounds,
and a physical attack through salt crystallization.
4.3. Gypsum formation (compressive strength reduction and mass
loss)
The second form of sulfate attack occurs from the formation of
gypsum, resulting in loss of material, strength and stiffness. The
chemical reactions of Portland cement-sodium sulfate system
leading to gypsum formation were given in the earlier section.
4.3.1. Compressive strength reduction
The compressive strength of the studied mixtures were
measured after 180 and 360 days exposure to sulfate solution
and their results are reported in Table 4. It can be observed that,
although minimal in nature, continuous sodium sulfate immersion
provided an environment less conducive to gypsum-based attack
than that of the cyclic sodium sulfate immersion. The strengths
of concretes exposed to both types of sulfate immersion were mar-
ginally higher than strength of those cured in standard conditions.
In order to highlight the observed behavior, the test results are
also presented in Figs. 4 and 5 for the age of 180 and 360 days,
respectively. On average, the 180-day compressive strengths of
cyclic-immersed and continuously-immersed samples were 5.0%
and 5.6% higher than those of water-cured samples. These
increases were 4.3% and 5.3% for one-year compressive strengths,
respectively. The fact that no compressive strength loss was
observed during the severe continuous sodium sulfate immersion
may be attributed to the same reasons reported in the earlier
sections. The compressive strength improvement during the
sodium sulfate exposure over the water curing may be attributed
Fig. 5. 360-day compressive strength of the mixtures under standard curing
condition and sulfate immersion.
to the built-up of sulfate reaction by-products (or ettringite com-
pounds), which act as a filler to improve concrete resistance.
It can also be seen in Fig. 4 that the 180-day strength was
increased up to 15, 20 and 25% replacement levels for cementitious
materials contents of 333, 374 and 416 kg/m3, respectively. The
compressive strength then decreased by increasing the replace-
ment levels. The picks were at 20, 25 and 30% for 360-day
compressive strengths as shown in Fig. 5. As the trend was similar
to that of water-cured samples, this behavior may be similarly
attributed to the depleted source of calcium hydroxide which lim-
ited the role of the excess fly ash to merely fill the micro voids of
concrete matrix.
4.3.2. Mass loss
After 360 days of continuous and interrupted cyclic sodium
sulfate immersion, none of the trial concretes showed any signs
of deterioration in the form of mass loss, indicating little or no
gypsum softening throughout the experiment.
5. Failure criteria and sulfate resistance classification
Although various failure criteria have been proposed over the
past sixty years, there is no universally acceptable failure criterion
for concrete exposed to sulfate-rich environment. Common
methods of evaluation include strength loss, change in dynamic
modulus of elasticity, expansion, loss of mass, and visual inspec-
tion. Miller and Manson [22] proposed a 0.02% expansion limit to
classify failure of specimens exposed to a 1% solution of sodium
sulfate. Stark [23] devised a visual rating scale for evaluation of
concrete. Ratings were based on a scale of 1.0–6.0, with the upper
limits indicating failure. Mather [24] suggested 0.1% increase in
length as a failure criterion for a test procedure standardized as
ASTM C 1012 [19]. Mehta and Monteiro [5] set a failure limit based
on strength reduction for cement paste, with a drop of strength of
more than 25% indicating poor performance. ASTM subcommittee
C 01.29 on sulfate resistance suggested performance limits for
mortar bars tested under ASTM C 452 [25] and ASTM C 1012
[19]. The limits are: at the age of 14 days (C 452, [25]) and six
months (C 1012, [19]), specimens with expansion of less than
0.06% and 0.1%, respectively, are considered to have ‘‘moderate sul-
fate resistance,’’ whereas those with less than 0.04% and 0.05%,
respectively, have ‘‘high sulfate resistance.’’ Other failure criteria
have been proposed, each based on different variables such as type
of specimen and type of exposure.
While the role of ASTM Type V cement in the reduction of
external sulfate attack in concrete is well established, the results
 N. Ghafoori et al. / Construction and Building Materials 78 (2015) 85–91
of this study were compared with the recommendation of ASTM
subcommittee C01.29 (Mather, [24]) in order to gain an insight
into the rating of sulfate resistance. Based on the six-month
expansion limit recommended by ASTM C 1012 [19], all the
studied concretes displayed expansion well below 0.05% and, thus,
can by classified as having ‘‘high sulfate resistance.’’ Moreover,
Mehta’s recommended 25% strength loss limit for sulfate-resistant
concretes was also met by all trials matrices.
6. Conclusions
Based on the results of the investigation, the main conclusions
are as follows:
1. The major rate of expansion of the studied concretes was
observed during the first 2 months of immersion. The rate of
expansion reduced throughout the remainder of the immersion
period due to the steady exhaustion of tricalcium aluminates
(C3A) and the built-up of ettringite compounds (C6AS3H32).
2. Replacing a portion of Type V cement with fly ash was effective
in improving sulfate resistance of the studied concretes. The
improvements, however, were not as much as anticipated as
they hardly exceeded 15% under their best performance.
3. The optimum replacement levels of Type V cement with fly ash
was different for different cementitious materials contents.
They were increased with increases in cementitious materials
contents. Fly ash replacement levels of 15, 20 and 25% led to
the lowest expansion and the highest strength for cementitious
materials contents of 333, 374 and 416 kg/m3, respectively.
4. No mass loss and strength reduction were observed within a
year of exposure in both immersion types. The continued
expansion and the absence of mass loss or noticeable reduction
in strength may be attributed to the presence of ettringite com-
pounds with no to minimal contribution from gypsum
formation.
5. The compressive strength and expansion of the studied con-
cretes under interrupted sulfate immersion condition were
marginally lower than those of continuously immersed sam-
ples. The compressive strengths of samples under both sulfate
immersion types were slightly higher than those of equivalent
water-cured concretes.
Acknowledgements
This study was made possible by the financial contribution of
Southern Nevada Concrete and Aggregate Association (SNCAA).
Thanks are also extended to a number of producers and manufac-
turers for providing materials used in this investigation.
91
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