Construction and Building Materials 25 (2011) 29882996

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Construction and Building Materials

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Resistance of plain and blended cement mortars exposed to severe sulfate attacks
Thidar Aye a,, Chiaki T. Oguchi b
a
b

Department of Civil and Environmental Engineering, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, Japan
Geosphere Research Institute, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama 338-8570, Japan

a r t i c l e

i n f o

Article history:
Received 28 June 2010
Received in revised form 17 September 2010
Accepted 13 November 2010
Available online 14 January 2011
Keywords:
Physical sulfate attack
Chemical sulfate attack
Silica fume
Fly ash
Diatomaceous earth

a b s t r a c t
To emphasize the effect of physical sulfate attack on pozzolanic additions, the resistance of plain and
blended cement mortars was investigated using 10% Na2SO4 and MgSO4 solutions under four exposure
regimes which included the standard conventional exposure and eld-like exposures that created the
physical sulfate attack. Although the performance of blended cement mortars was observed to be better
under a conventional exposure regime, the damage in blended cement mortars was more severe under
the exposure regimes that promoted the physical sulfate attack in a Na2SO4 environment. However,
the physical attack by MgSO4 was not apparent. Overall, MgSO4 was found to be more damaging than
Na2SO4 from the aspect of chemical attack; however Na2SO4 was more harmful than MgSO4 as far as
the physical attack is considered.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
It is well established that sulfate ions from ground water, soil,
and seawater attack concrete and other cement-based materials.
Sulfate attack can be categorized as chemical attack and physical
attack according to their different attacking mechanisms. The
chemical attack arises from a series of chemical reactions between
sulfate ions and cement hydration products or cement components. In the so-called physical sulfate attack, also termed as salt
weathering, repetitive crystallization of sulfate salts under certain
environmental changes generates pressures against the pore wall
which lead to surface scaling of concrete structures. Such distress
has been observed in above-ground components of eld structures
[1]. Sulfate attack studies have a long history; however, researchers
have often focused on the chemical sulfate attack and physical sulfate attack has received little attention.
From the standpoint of chemical attack, the deterioration of
Portland cement concrete is partially or primarily due to the presence of CH (calcium hydroxide) which is the most vulnerable
hydration product to sulfate attack [2]. The use of pozzolans has
improved the sulfate resistance of concrete/mortar by chemically
reacting with CH and thereby reducing CH content. Moreover,
the pozzolan addition can rene the pore size of concrete/mortar,
which reduces the permeability and thereby reducing the ingress
of aggressive ions. However, from the standpoint of physical

Corresponding author. Tel.: +81 48 858 3568; fax: +81 48 855 1378.
E-mail address: s07de057@mail.saitama-u.ac.jp (T. Aye).
0950-0618/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2010.11.106

sulfate attack or salt weathering, the materials with ne pore size

are prone to salt crystallization damage. Thus, there is a concern
that concrete with pozzolan could be more vulnerable to this physical distress. This link is worthy to investigate the resistance of
blended cement mortars/concretes incorporated with pozzolans
against physical sulfate attack.
Besides, the current standard tests (such as ASTM C1012) overlook the physical attack that reects the actual eld conditions [3].
The eld structures are suffering from the effect of wetting and
drying due to water level uctuation, e.g., by ooding, rainwater
runoff and tides, and cyclic migration of sulfate-containing ground
water into the above ground portion of concrete structures by capillarity. Such processes result in the crystallization of sulfate salts
beneath the concrete surface layer. This causes cracking, scaling,
and delamination of the concrete surface. These damaging
phenomena cannot be captured by the continuous immersion
exposure used in current testing methods. Thus, there is a need
to provide essential knowledge on the performance of concrete/
mortar in different exposure conditions that can be indicative of
eld conditions.
Recently, research on physical sulfate attack has become an
important issue in sulfate attack studies. Nehdi and Hayek [4] have
studied the effect of humidity changes on the development of salt
eforescence on the specimens subjected to the partial immersion
exposure. It was a short-term test and thus the specimens did not
show any damages due to the formation of salt eforescence.
However, the study showed that responses of NaSO4 and MgSO4
solutions to environmental changes vary. In another study, Sahmaran et al. [5] investigated the effect of wettingdrying and
heatingcooling on the sodium sulfate resistance of plain and

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T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

blended cements. The study revealed the inferior performance of

blended cements incorporated with y ash, natural pozzolan, and
limestone exposed to wettingdrying and heatingcooling environment, although they showed a better performance in continuous immersion exposure. In a recent study by Haynes et al. [6],
the concrete specimens made with ASTM Type II Portland cement
were subjected to partial immersion in 5% Na2SO4 solution and the
effect of temperature and humidity cycles simulating various
ambient conditions was examined. The study showed that
concrete scaling occurred at evaporation surfaces and it was significant when the specimen was subjected to repetitive crystallization of thenardite (Na2SO4) and mirabilite (Na2SO4
10H2O).
However, there are still few studies about physical sulfate attack, especially on the addition of pozzolans. The objective of this
study is to evaluate the sulfate resistance of mortars made with
plain cements and blended cements incorporated with well-known
active pozzolans: silica fume, y ash and a natural pozzolan, namely
diatomaceous earth, under different exposure regimes. In addition
to the conventional exposure, the exposure regimes that may exist
under eld conditions were implemented to fulll the objective.
2. Experimental details
2.1. Materials
A normal Portland cement and a sulfate-resisting Portland cement were used to
make the plain cement mortars (henceforth abbreviated as NPC and SRPC, respectively). In addition, three types of blended cement mortars were prepared by replacing a part of normal Portland cement with 25% y ash, 8% silica fume, and 8%
diatomaceous earth by weight (henceforth abbreviated as FA, SF and DE, respectively). These pozzolans are commercially available in Japan. Properties of cements
and pozzolans are given in Table 1. Chemical compositions were determined by Xray uorescence (XRF) and compound compositions were calculated using Bogue
equation. The replacement levels of y ash and silica fume were adopted based
on Nehdi and Hayek [4]. As the porous diatomaceous earth particles require a high
water content, 8% replacement level was selected based on its water demand. The
aggregate used for the mortar mixtures was quartz sand with a neness modulus of
2.83 and a specic gravity of 2.66.
In all mortar mixtures, the sand:cement ratio was kept constant as 2:1 by
weight. A naphthalene sulfonate-based superplasticizer was added to the mixing
water at a dosage of 0.8% by mass of binder in mortar mixtures made with a w/c
ratio of 0.45. The paste samples used for the determination of sulfate reaction products were prepared with no superplasticizer. Mortar and paste specimens were
demoulded after casting in the moulds for 24 h. The specimens were then cured
in tap water at 20 C for 27 days.
To assess the pore characteristics of the mortars, an Autopore IV 9500 Micromeritics mercury intrusion porosimeter (MIP) was used. A representative mortar
sample of about 5 mm in size was selected for this test. These small specimens were
pre-dried at 105 C and cooled down in a desiccator before they were subjected to
MIP analysis. The pore size distribution measured by MIP is shown in Fig. 1. The

blended mortars have ner pore structures compared to the plain mortars. The
NPC and SRPC mortars mainly consist of larger pores of 0.08 lm in diameter. The
FA and SF mortars have a signicantly ner pore structure relative to that of other
mortars. The DE mortar has the lowest intruded pore volume, but the volume of
small pores (<0.05 lm in diameter) in DE mortar is higher than that in NPC and
SRPC mortars.

2.2. Testing methods

From each mortar mixture, 5 cm cubic specimens and 5 cm  5 cm  12 cm
prismatic specimens were prepared for the tests. For all tests, 10% Na2SO4 and
10% MgSO4 were used as attacking solutions. The performance of plain and blended
cements under sulfate attack was determined by the loss in the compressive
strength of cubic specimens according to ASTM C1012. Fifteen specimens of each
mortar were immersed in 10% Na2SO4 and another 15 specimens were immersed
in 10% MgSO4 solution. For a reference, another 15 specimens were stored in tap
water. The compressive strength of ve specimens was measured at 8, 16 and
24 weeks after they were placed in the respective solutions. Then, the strength loss
was calculated based on the compressive strength of mortar specimens immersed
in tap water.
In addition, the cubes or prisms were subjected to four different exposure regimes to emphasize the physical sulfate attack:
 Exposure I (continuous full immersion at a constant temperature): Five cubic specimens were continuously submerged in each sulfate solution at 20 C for
24 weeks.
 Exposure II (full immersion under cyclic wetting and drying): Five cubic specimens
were exposed to cyclic drying and wetting in each sulfate solution. The cycle
consisted of immersion, drying, and cooling phases. Each cycle was composed
of full immersion in sulfate solution at 20 C for 94 h, oven drying at 50 C for
72 h, and cooling in air at 20 C for 2 h. Such one-week repeat cycles were
run for 24 times.
 Exposure III (continuous partial immersion at a constant temperature): Three prismatic specimens were continuously subjected to partial immersion in each 3cm deep sulfate solution at 20 C for 16 weeks in which their minor base rested
against the container containing a sulfate solution.
 Exposure IV (partial immersion under cyclic wetting and drying): Three prismatic
specimens were partially immersed in sulfate solutions in a way similar to
exposure III, but they were exposed to the same wetting and drying cycles similar to exposure II described above. This exposure continued for up to 16 cycles.
The humidity was uncontrolled, but recorded in all tests. The performance of
specimens in each exposure regime was visually inspected throughout the test.
Exposures IIIV were selected to promote physical sulfate attack. The mass loss
due to surface scaling and delamination was an observable damage mode by physical attack in eld structures. Thus, the weight loss measurement is the best indicator of degree of deterioration in laboratory experiment. In this study, the weight of
the specimens was measured and the weight loss was calculated based on their initial weight at the end of exposure periods. In exposures I and II, the paste specimens
were exposed to the same conditions with the mortars to investigate the reaction
products. Then the reaction products were detected by X-ray diffraction (XRD) analysis. Also, the salt eforescence developed in specimens in exposures III and IV was
characterized by XRD analysis to support the explanation of deterioration process.
The XRD analysis was conducted on powder sample using a RINT-Ultima III (Rigaku) X-ray diffractometer with Cu Ka radiation.

Table 1
Properties of cements and pozzolans.

Chemical composition (%)

SiO2
CaO
Al2O3
Fe2O3
SO3
MgO
LOI
Physical propertiesa
Specic gravity
Specic surface area
(cm2/g)
Mineral composition (%)
C3S
C2S
C3A
C4AF
a

Normal Portland
cement

Sulfate-resisting Portland
cement

Fly
ash

Silica
fume

Diatomaceous
earth

21.43
64.51
5.28
2.96
2.09
0.9
1.81

22.04
64.98
3.28
4.61
1.89
0.6
0.89

63.3
2
26.3
3.4
0.6
0
1.22

95.5
0.3
0
1.4
0.18
0.56
1.1

89.2
0.9
6.2
2.4
0
0.8
0.2

3.16
3300

3.20
3200

2.38
3350

2.02
180,000

2.25
35,000

54
21
9
9

63
16
0.9
14

The data were supported by manufactures.

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T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

Fig. 1. Pore size distribution of mortars.

3. Results and discussion

3.1. Performance of plain and blended cements
The performance of plain and blended cements under conventional sulfate attack was monitored for 24 weeks through measurement of compressive strength loss of mortar specimens, and
the results are presented in Fig. 2. A decrease in strength, with a
period of exposure, was noted in all types of mortars in both
Na2SO4 and MgSO4 solutions. A higher reduction was noted in
NPC mortar, followed by SRPC and FA after 24 weeks of Na2SO4
exposure. SF mortar exhibited the best resistance to Na2SO4 attack.
Nonetheless, the strength loss was the highest in SF mortar followed by DE mortar after 24 weeks of MgSO4 exposure. The minimum strength loss was noted in SRPC mortar.
A lower strength loss was observed in blended cement mortars
than in plain cement mortars in Na2SO4 solution. This may be
attributed to a reduction in the quantity of both CH and C3A (which
is a major source of formation of ettringite), thereby to a reduction
in deleterious compounds such as gypsum and ettringite. However,
the blended cement mortar displayed less resistance to MgSO4 attack compared to NPC mortar. This behavior was due to the fact

that the reduced CH content in the blended cement mortars

favored the MgSO4 attack toward the CSH [3,7]. As a result,
the decomposition of CSH was accelerated and that led to a
greater strength reduction. The same can be claimed for the
minimum strength loss observed in SRPC mortar. According to
the results, the use of pozzolan is not suitable for MgSO4 environment. These results were in line with the ndings of many previous
researches.
In Na2SO4 environments, expansion and cracking due to the
formation and gypsum and ettringite are primary deterioration of
cement-based materials. However, in the case of MgSO4 attack,
the strength loss due to the decalcication of CSH is the major
cause of deterioration. Therefore, it is said that MgSO4 is more
damaging than Na2SO4 [1] from the aspect of chemical attack. In
this study, the strength loss of mortars under MgSO4 attack was
observed to be higher than that under Na2SO4 attack due to different attacking mechanisms.
3.2. Exposure I: Continuous full immersion at a constant temperature
The damage was rst observed in NPC mortar in the form of
spalling along the edges of the specimens at 12 weeks of Na2SO4

Fig. 2. Compressive strength loss of mortars exposed to sulfate solutions in exposure I.

T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

exposure. Then, a similar form of damage was noted in SRPC

mortar at 14 weeks and FA mortar at 20 weeks. The damage in
FA mortar was somewhat less. DE and SF mortars behaved in the
same way with no visible damages up to 24 weeks of exposure.
As indicated in Fig. 3, typical compounds associated with sulfate
attack, such as ettringite and gypsum, were detected in NPC and
SRPC pastes exposed to Na2SO4 solution. SF and DE pastes showed
no gypsum peaks, and only a somewhat-weak ettringite peak was
observed. Thus, little or no visual damage occurred in blended cement mortars was attributed to the reduction of CH content by
pozzolanic reactions, which thus reduced the potential for the formation of deleterious ettringite and gypsum.
Besides the loss of cohesionless particles from the surface of the
specimens, no other damages (such as cracking and spalling) were
observed in all types of mortars in the MgSO4 environment.
Although ettringite is formed during the reaction of MgSO4 with
CH, it cannot be stable in low pH environments. The saturated
solution of brucite (that is also formed by the reaction of MgSO4
with CH) having a pH of about 10.5 causes the destabilization of
ettringite [8]. In this study, ettringite was not observed in the
pastes (Fig. 4). Accordingly, deterioration such as cracking and
spalling by ettringite could not be found in the mortar specimens
exposed to MgSO4 solution. Instead, a loss of cohesionless particles
was observed. This was attributed to gypsum formation and decalcication of CSH (i.e., decomposition of CSH to non-cementitious MSH). Due to this surface corrosion, the weight loss of
the specimens exposed to MgSO4 solution was higher than that
of those exposed to Na2SO4 solution (Table 2).
It is noticeable that the weight loss of blended cement mortars
was less than that of plain mortars in the Na2SO4 environment.
However, it was found that the amount of weight loss was less
than 1% for all types of mortars. Therefore, the measurement of
weight change is not an appropriate deterioration measure for
Na2SO4 attack. On the contrary, the weight loss of blended mortars
was observed to be higher than that of plain mortars in the case of
MgSO4 attack. The maximum weight loss was noted in SF mortar

2991

Fig. 4. XRD patterns of paste samples exposed to MgSO4 for 24 weeks (G: gypsum,
CH: Ca(OH)2).

followed by DE and FA mortars after 24 weeks of MgSO4 exposure.

SF and DE mortars exhibited a weight loss which was more than
the 2.5% failure criterion for paste specimen as reported by Cohen
and Bentur [9]. The signicant weight loss of specimens treated
with MgSO4 solution was attributed to the loss of cohesionless
granular mass. Therefore, monitoring the weight loss seems to be
suitable measure to assess the performance of cement mortars in
MgSO4 environment. According to these results, the performance
of blended cement mortars was better in Na2SO4 solutions. However, it was relatively poor in MgSO4 solution when compared to
the plain cement mortars.

3.3. Exposure II: Full immersion under cyclic wetting and drying

Fig. 3. XRD patterns of paste samples exposed to Na2SO4 for 24 weeks (E:
ettringite; G: gypsum; CH: Ca(OH)2).

There was no sign of damage in all specimens treated with

Na2SO4 solution until 16 cycles of exposure II. The rst sign of
damage was observed in SF mortar at 17 cycles, FA mortar in 19 cycles and DE and NPC mortars at 20 cycles while no damage occurred in SRPC mortar until the end of 24 cycles. As shown in
Fig. 5, the maximum damage in the form of cracking and spalling
was observed in SF mortar followed by FA, DE and NPC mortars.
Also, the maximum weight loss was observed in SF mortars followed by FA and DE mortars at the end of 24 cycles (Table 2).
According to these results, the performance of blended cement
mortars in exposure II was poor compared to that of plain cement
mortars. It was contrary to the results of exposure I in Na2SO4
environment.
The repetitive crystallization of sodium sulfates due to wetting
and drying was believed to be a controlling damaging process in
exposure II. The phase changes of Na2SO4 can occur in cycling temperature and relative humidity. According to the phase transition

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T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

Table 2
Weight loss (%) of mortar specimens.
Weight loss (%) at 24 weeks
Exposure I

NPC
SRPC
FA
SF
DE

Weight loss (%) at 16 weeks

Exposure II

Exposure III

Exposure IV

Na2SO4

MgSO4

Na2SO4

MgSO4

Na2SO4

MgSO4

Na2SO4

MgSO4

0.85
0.81
0.72
0.49
0.52

1.92
1.96
2.42
3.91
3.23

3.47
2.28
5.62
7.03
4.06

1.00
1.15
2.23
2.60
2.68

1.36
1.10
0.74
0.44
0.49

1.59
1.65
2.24
3.65
3.51

3.18
2.09
17.95
20.53
8.33

2.23
2.36
2.81
4.46
3.56

Fig. 5. Visual appearance of (a) NPC, (b) SRPC, (c) FA, (d) SF and (e) DE mortar specimens exposed to Na2SO4 in exposure II for 24 cycles.

of Na2SO4 in relation to environmental changes proposed by Flatt

[10], thenardite (Na2SO4) was expected to crystallize in pores near
the exposed surfaces when the specimens were dried at 50 C.
When these salt crystals accumulated and concentrated in
sufcient amounts, a crystallization pressure may generate against
the pore wall which leads to the disintegration of the surface layer.
When the specimens containing thenardite was exposed to sulfate
solutions for rewetting at 20 C, the dissolution of thenardite and
consecutive precipitation of mirabilite (Na2SO4
10H2O) were
believed to occur. The precipitation of mirabilite generates high
crystallization pressures that are sufcient to damage the
specimens during rewetting [10]. Such repetitive crystallization
of thenardite and mirabilite due to cyclic wetting and drying was
responsible for the deterioration of mortar specimens exposed to
Na2SO4 solution.
Salt crystallization damage is closely related to the pore size.
The damaging crystallization pressure generates in small pores
[11]. It was evident that salt crystallization caused signicant
destructive consequences with respect to cracking and spalling in
mortars with a very ne pore structure (i.e., SF and FA mortars as
shown in Fig. 1). It seems that salt crystallization led to extensive

cracking that allowed further penetration of the solution and accelerated the attack in mortars with a ne pore structure.
In the case of MgSO4 attack, all types of mortar specimens were
found to be intact up to 24 cycles. It was found that the weight
loss was higher in blended cement mortars than in plain cement
mortars and the SF mortar displayed the maximum weight loss
in MgSO4 environment (Table 2). There was no evidence of
crystallization damage in mortar specimens and a similar damage
pattern of surface corrosion to exposure I was observed. Thus, that
feature of deterioration was mainly attributed to the chemical
attack.
MgSO4 has anhydrous (MgSO4) and hydrous phases (epsomite:
MgSO4
7H2O, hexahydrate: MgSO4.6H2O, kieserite: MgSO4
H2O).
According to the environmental conditions for phase transition of
MgSO4 [12], an anhydrous phase of MgSO4 will not precipitate
up to 80 C. And, the dehydration of hexahydrate is possible at
temperatures above 70 C. In this study, the crystallization of
hexahydrate was expected in the drying period and epsomite
would precipitate when the specimens were exposed to solution.
However, this transition involves the change in one hydrate
(MgSO4
7H2O M MgSO4
6H2O) and thus may not generate as much

T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

stress as thenarditemirabilite transition (Na2SO4 M Na2SO4

10H2O). Furthermore, it seems that mirabilite precipitates
faster than epsomite during the immersion period. Since salt
crystallization speed denes the extent of damage, the Na2SO4
hydrate system can be more destructive than the MgSO4 hydrate
system.
Similar to exposure I, the sulfate reaction products were
detected in paste specimens exposed to drying and wetting in both
sulfate solutions, but the intensity of peaks for these products was
weak compared to that found in exposure I. This may be because of
the fact that the sulfate exposure period (4 days in a week) in
exposure II was shorter than that in exposure I. Besides, salt
crystals formed in the pores during the drying period would
block the solution penetration to some extent in the immersion
period.

Fig. 6. Typical salt eforescence development by (a) Na2SO4 and (b) MgSO4 in
exposure III at 16 weeks.

2993

3.4. Exposure III: Continuous partial immersion at a constant

temperature
Fig. 6 shows the typical appearance of mortar specimens treated
with exposure III. In Na2SO4 environment, thick salt eforescence
was developed in all types of mortars. These eforescences occurred at the early age of sulfate exposure and they reached the
top of specimens within 4 weeks. In MgSO4 solution, a thin layer
of eforescence occurred just above the solution level in all specimens until the end of 16 weeks. After 16 weeks of sulfate exposure,
the salt eforescence was removed and the damage in mortar specimens was inspected. No signicant damage was observed in all
types of mortars in both solutions. Although the specimens did
not show any visible damages, the loss of cohesionless particles
from the immersion portion of the specimen led to the weight loss
in the specimens. The weight loss of specimens in MgSO4 solution
was found to be higher than that in Na2SO4 solution (Table 2). The
weight loss in blended cement mortars was greater in MgSO4 solution, but it was lesser in Na2SO4 solution compared to plain cement
mortars. These ndings were similar to the results of exposure I
and thus it was believed that the weight loss was due to the chemical attack rather than the salt crystallization.
In MgSO4 solution, the capillary rise was just above the solution
level while the solution rose to the top of the specimen that was
exposed to Na2SO4 solution (Fig. 6). That was due to the different
physical properties of sulfate solutions. At 20 C, the viscosity of
saturated Na2SO4 is 1.834 cP while that of saturated MgSO4 solution is 7.270 cP [13]. Therefore, the capillary ow was slower in
the case of MgSO4 solution because of its higher viscosity.
In this exposure regime, the environmental relative humidity
(RH) was normally changing between 45% and 70% at a constant
temperature of 20 C. But the maximum RH of 80% and the minimum RH of 40% were rarely recorded. The RH increase up to 80%
can lead to thenarditemirabilite transition and the RH decrease
up to 40% can cause epsomitehexahydrate transition [10,12].
However, this transition cannot occur on the surface and beneath
the surface of the upper portion (not exposed to the sulfate solution) of the specimens. That was because the specimen surface
was damp due to the continuous solution support from the bottom
portion (immersed portion) of the specimen. Therefore, the eforescence formed on the surface was observed as mirabilite by
XRD analysis (Fig. 7) although the environment (45% < RH < 70%)

Fig. 7. Typical XRD pattern of eforescence showing a pattern of mirabilite.

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T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

was supportive of a thenardite formation. However, the eforescence was detected as thenardite only at approximately 0.5 cm
away from the specimen surface (Fig. 8). Similarly, epsomite was
detected on the surface of the specimen that was exposed to
MgSO4 solution (Fig. 9). Therefore, the salt crystals formed within
the porous materials cannot be inuenced by the changes in environmental relative humidity in this type of exposure regime. Nonetheless, salt crystallization alone (without involving phase
transition), e.g., mirabilite crystallization [6], can cause the scaling
damage. However, long-term exposure may be necessary to obtain
the signicant damage by salt crystallization alone.
3.5. Exposure IV: Partial immersion under cyclic wetting and drying
Fig. 10 shows the appearance of mortar specimens treated with
Na2SO4 solution in exposure IV at the end of 16 cycles. The salt
eforescence developed in the upper portion of the specimen
(not exposed to sulfate solution) during the immersion period
and some of these eforescences were detached during the drying
period. At a later age of wettingdrying cycles, the mortar components were also detached along with the salt eforescence and
thus the specimens showed marked visual features of deterioration. On contrary, the salt eforescence occurred just above the

solution level during the course of immersion in MgSO4 solution

(Fig. 11). After removing the salt eforescence at the end of 16 cycles, the maximum deterioration was observed in SF mortar followed by FA and DE mortars treated with Na2SO4 solution
(Fig. 12). Correspondingly, the maximum loss of weight was observed in SF mortar followed by FA and DE mortars in Na2SO4 environment (Table 2). However, no visible features of damage were
found in specimens treated with MgSO4 solution. SF mortar displayed the maximum weight loss in MgSO4 solution. It was found
that the weight loss of blended mortars was greater than that of
plain mortars in both solutions. The weight loss in Na2SO4 was
attributed to salt crystallization; however, in MgSO4 it was caused
by the chemical attack to the immersed portion of specimen.
As have discussed for aftermath of exposure II, the repeated
transition of thenardite and mirabilite due to cyclic wetting and
drying exposure was attributed to the severe damage in specimens
exposed to Na2SO4 solution. During the immersion period, only
mirabilite formation was possible at or beneath the surface of
upper portion of specimen (regardless of the changes in ambient
RH) and the salt eforescence converted to thenardite during the
drying period. It was conrmed in XRD analysis that the eforescence occurred during the drying period was composed of thenardite. The damage was more severe in mortars with ne pore

Fig. 8. Typical XRD pattern of eforescence showing a pattern of thenardite.

Fig. 9. Typical XRD pattern of eforescence showing a pattern of epsomite.

T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

Fig. 10. Typical appearance of specimens treated with Na2SO4 in exposure IV, (a)
after the immersion period and (b) after the drying period.

structures (i.e., SF and FA mortars). Also, DE mortar had a minimum intruded pore volume (Fig. 1), but the volume of smaller
pores (pore diameter < 0.05 lm) in DE mortar was higher than that
in NPC and SRPC mortars. Accordingly, the visible damage was signicant in DE mortar while little damage was observed in NPC and
SRPC mortars. According to these results, the use of pozzolan is not
suitable for an environment that is favorable for salt crystallization. However, the pore structure in mortar or concrete is modied
by w/c ratio and replacement level of pozzolanic admixtures. Thus,
further researches are needed for a better understanding of the
effect of w/c ratio and pozzolan replacement level on the physical
attack under the eld-like exposure conditions.
The change in temperature from 20 C to 50 C in this exposure
regime would lead to the epsomitehexahydrate transition.
However, the salt crystallization damage was not apparent. The
destructive crystallization pressure is highly related to the degree

2995

Fig. 11. Typical appearance of specimens treated with MgSO4 in exposure IV, (a)
after the immersion period and (b) after the drying period.

of supersaturation of the solution [14]. On the other hand, the degree of supersaturation in a porous medium is different for different salt solutions at a same temperature. As a result, the
destructive power of Na2SO4 and MgSO4 is different at a same
experimental condition. This study showed that MgSO4 was less
harmful than Na2SO4 under this experimental temperature. Overall, the potential damage by the physical attack depends on not
only the pore size in mortar but also the thermodynamic response
of salt solution to ambient environmental temperature.
It was also observed that exposure IV was more severe than
exposure II regardless of different test periods. These results can
be related to the solution accessibility and mobility in porous
media. In exposure II, air bubbles that partially existed in the pores
inside the specimens could act as an obstacle to the solution
penetration from all directions. As the upper portion of the

Fig. 12. Typical appearance of (a) NPC, (b) SRPC, (c) FA, (d) SF and (e) DE mortar specimens treated with Na2SO4 in exposure IV (after removing salt eforescence at 16 cycles).

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T. Aye, C.T. Oguchi / Construction and Building Materials 25 (2011) 29882996

specimen was exposed to air and the solution penetration was by

capillary action in exposure IV, air bubbles could be expelled easily
and thus a great quantity of solution was able to enter the porous
media. On the other hand, salt crystals growing from a supersaturated solution must be conned in a pore space (i.e., the growing
crystals must be completely lled a pore) to generate the destructive pressure against the pore wall [14]. In the case of exposure IV,
crystal growing was possible in upper portion of specimen even in
the immersion period due to the presence of evaporative surface.
Thus, the salt crystal growth may be faster to completely ll the
pores in exposure IV. As a consequence, an earlier and greater deterioration was observed in exposure IV compared to exposure II.
Moreover, the physical attack (in exposure II or IV) was predominant compared to the chemical attack (in exposure I).
4. Conclusions
Sulfate resistance of plain and blended cement mortars were
investigated under different exposure regimes, which included
the standard conventional exposure and eld-like exposures. The
following conclusions were reached based on this experimental
study.
 The addition of pozzolan improved the resistance of mortar to
Na2SO4; however, it aggravated the consequence of MgSO4
attack from the standpoint of chemical attack.
 The performance of blended mortars with ne pore structures
was relatively poor under the cyclic wetting and drying exposure regimes in Na2SO4 environment. However, the physical
attack by MgSO4 was not apparent to both plain and blended
cement mortars.
 Overall, MgSO4 is more damaging than Na2SO4 from the aspect
of chemical attack; however, Na2SO4 is more harmful than
MgSO4 when the physical attack is considered.

Acknowledgements
This work has been supported by the Science Research Fund of
JSPS (No. 18680054). The authors wish to thank the members of
Structural Material Laboratory for their kind assistance in the preparation of mortars.
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