Durability of concrete under sulfate attack exposed to freeze-thaw cycles

Lei Jiang, Ditao Niu, Lidong Yuan, Qiannan Fei

PII: S0165-232X(14)00222-5
DOI: doi: 10.1016/j.coldregions.2014.12.006
Reference: COLTEC 2052

To appear in: Cold Regions Science and Technology

Received date: 23 July 2013

Revised date: 6 December 2014
Accepted date: 12 December 2014

Please cite this article as: Jiang, Lei, Niu, Ditao, Yuan, Lidong, Fei, Qiannan, Durability
of concrete under sulfate attack exposed to freeze-thaw cycles, Cold Regions Science and
Technology (2014), doi: 10.1016/j.coldregions.2014.12.006

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 ACCEPTED MANUSCRIPT

Durability of concrete under sulfate attack exposed to

freeze-thaw cycles

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Lei Jianga,b, Ditao Niub*, Lidong Yuanb, Qiannan Feib

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a
College of Civil Engineering and Architecture, Anyang Normal University, Anyang 455000,China
b
College of Civil Engineering and Architecture, Xi’an University of Architecture and Technology, Xi’an 710055,China

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* Corresponding author. Tel: +86 139 9113 1565; E-mail: niuditao@163.com.

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Address: College of Civil engineering, Xi’an University of Architecture and Technology, No. 13 Yanta Road, Xi’an, Shaanxi

710055, P.R. China

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Abstract: Properties of concrete (with additional 20% fly ash) subjected to freeze-thaw cycles in water
and in sulfate solutions were investigated in this paper. The corrosion solutions include two types,
namely, 5% sodium sulfate solution and 5% magnesium sulfate solution. Through the experiment,
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visual examination was conducted to evaluate the surface damage. The deterioration considering the
weight loss, relative dynamic modulus of elastically (RDME) loss and compressive strength loss of
concrete under the coupling effect were also investigated. To identify the products formed by sulfate
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attack, analytical techniques, including X-ray diffraction, scanning electron microscopy and thermal
analysis were performed on the selected samples after freeze-thaw circulations. Test results show that
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freeze-thaw cycles and sulfate attack affected each other. On the one hand, a lower temperature during
freeze-thaw cycles slows down the diffusion of sulfate ions in concrete. On the other hand, sulfate
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attack accelerates the formation of microcracks in concrete, which leads to more severe damage under
freeze-thaw cycles. The rate of damage in concrete is significantly dependent on the types of sulfate
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solutions, and the concrete deterioration by magnesium sulfate covers the most aggressive corrosion
subjected to freeze-thaw cycles. Furthermore, the compressive strength loss and RDME loss of
concrete in sodium sulfate solution is less than that in water during the initial freeze-thaw cycles, but
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the damage is more severe in further test period.

Keywords: Concrete; Freeze-thaw cycles; Sulfate attack; Microstructure

1. Introduction
External sulfate attack on cement-based materials and the deterioration of
concrete constructions resulting from freeze-thaw damage are the severe problems
affecting the durability and service life of concrete structures (Skalny et al., 2002;
Mehta, 1991). According to the related reports (Liu, 2001; Wang et al., 2001), there
exist a lot of sulfate-rich soils and more than 1000 salt lakes are scattered in
Northwest China. In such regions, a large number of concrete structures are severely
deteriorated and their service life is largely shortened, mainly because of the sulfate
attack and freeze-thaw damage. Thus, studying the damage process of the concretes in
these areas for a rapid development of the infrastructure in Northwest China is
necessary.
Many studies on the damage process of concrete exposed to sulfate attack
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(Ramyar et al., 2007; Al-Dulaijan et al., 2003; Wee et al., 2000) and the coupling
function of sulfate attack and drying-wetting cycles (Bassuoni et al., 2009a; Bassuoni
et al., 2009b; Jin et al., 2008) have been published. Scholars have acknowledged that
the dissolved sulfate salts can enter into chemical reactions with cement-based
materials causing expansion, cracking, spalling and disintegration. However, few

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studies of the entire process of damage have been conducted on concretes considering
the action of sulfate attack and freeze-thaw damage together. The interaction between

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freeze-thaw cycles and sulfate attack on the deterioration of concrete is not well
known. Miao et al. (2001) investigated the properties of plain concrete (PC) and steel

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fiber reinforced concrete (SFRC) (with a water/cement ratio of 0.44, 0.32 and 0.26)

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subjected to freeze-thaw cycles in 5% sodium sulfate solution, reporting that the
properties of SFRC are superior to that of PC and the decline in the RDME of SFRC
is significantly slower than that of PC. According to Yu et al. (2005; 2008), the

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freeze-thaw durability of concrete is visibly reduced exposed to the flexural stress in
salt solution and the stress, and chemical attack accelerates the damage process.
Zhang et al. (2011) studied the frost resistance of concrete under the action of
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magnesium sulfate attack, indicating that magnesium sulfate solution can significantly
alleviate the freeze-thaw damage for the high-strength concrete (HSC) with a higher
water binder ratio and a lower content of mineral admixtures because of lowering
effect of the magnesium sulfate solution freezing point. Zheng et al. (2010) claimed
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that not only physical changes but also chemical reactions occur in concrete under the
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combined actions of multi-aggressive (3% sodium chloride and 5% sodium sulfate)

and freeze-thaw environment, which can exacerbate the deterioration of the
mechanical properties of concrete.
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Most researches have focused on the single environmental factor affecting the
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deterioration of concretes, and little information is available about the interaction

between freeze-thaw cycles and sulfate attack. Furthermore, the microstructural
features of concrete under the coupling effect require further investigation. In this
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paper, basic experimental research on the performance of concrete subjected to

freeze-thaw cycles in water and in the sulfate solutions was conducted based on the
macroscopic and microscopic test. The effect of sulfate solution on the deterioration
of concrete under freeze-thaw cycles was also analyzed.

2. Experimental details

2.1. Materials and mix proportions

A Chinese standard Ordinary Portland Cement (OPC) of PO 42.5R produced by

the Cement Factory of Tongchuan was adopted. Grade II fly ash from the Weihe
Power Station, river sand with a fineness modulus of 2.69 and coarse aggregate of
crushed basalt stone with a diameter of 5 mm to 16 mm were used in the test. A
naphthalene-type superplasticizer was used, and the dosage was adjusted to keep the
slump of fresh mixed concrete in the range of 50 mm to 120 mm. The SJ-3
air-entraining agent provided by Tongji University is a type of gleditsia sinensis made
from plants. The air content of fresh mixed concrete was measured according to
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ASTM C231. The chemical composition of cement and fly ash is shown in Table 1.
In this experiment, the water-binder ratio (W/B) was 0.45, and the concrete with
20 wt.% replacements of cement with fly ash was used. According to the related
investigations (Al-Dulaijian et al., 2003; Jin et al., 2007; Chen et al., 2012), about 20
wt.% of cement is replaced by fly ash, the resistance property of concrete to sulfate

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attack could be improved effectively. The mixture proportion and corresponding
compressive strength of the concrete are presented in Table 2. The mixture proportion

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used in the paper was developed for the laboratory investigation.

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Table 1 Chemical composition of OPC and fly ash
----Insert Table1----

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Table 2 Mix proportion and compressive strength of concrete
----Insert Table2----

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2.2. Specimens preparation and curing conditions

Concrete specimens were prepared in a 0.3 m3 forced action mixer, and all the
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test specimens were fabricated from a single batch of concrete. The components of the
concrete mixture were batched by weight, the cement was premixed with fly ash, sand
and coarse aggregate before adding the water and the admixtures for 1 minute. Then,
the entire amount of mixing water with the dissolved superplasticizer and air
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entraining agents were added and mixed for 3 minutes. Finally, concrete mixture was
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mixed for another 2 minutes. The concrete specimens were cast in steel moulds and
compacted on a vibration table. All specimens were demolded after 24 hours of
casting and were cured in a condition of 20 ± 3 °C and 95% relative humidity.
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2.3. Test methods

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2.3.1. Freezing and thawing cycle tests

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In this study, the cyclic freeze-thaw test was conducted in the accelerated
freeze-thaw testing apparatus according to GB/T50082 (2009). The temperature of the
concrete samples was controlled by a Pt (platinum thermal) sensor embedded in the
center of a 100 mm×100 mm×400 mm prism specimen. The temperature of the
sample center ranged from –18 ± 2 °C to 5 ± 2 °C. In a single freeze-thaw cycle, the
temperature of the specimens cools from 3 °C to −16 °C and then warms to 3 °C all
within approximately 2.5 hours to 4 hours. The freezing time should not exceed three
quarters of the freezing and thawing time. The time of the temperature cools from
3 °C to −16 °C should not be less than one half of the freezing time, and the time of
the temperature warms from −16 °C to 3 °C should not be less than one half of the
thawing time. In the test, specimens were frozen and thawed in the liquid solution.
The solution test for freeze-thaw cycles includes the following types: water,
sodium sulfate and magnesium sulfate solution. In this study, concentrations of 5%
sodium sulfate solution and 5% magnesium sulfate solution (by mass) were used
(Zhang et al., 2011; Shanahan et al., 2007). The specimens were cured for 86 days,
and then immersed in the three solutions for 4 days, respectively. At the age of 90
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days, the testing of concrete exposed to freeze-thaw cycles in three different solutions
was conducted. For each case, 3 specimens of 100 mm×100 mm×400 mm prisms and
39 specimens of 100 mm cubes were used to examine the weight loss, RDME loss
and compressive strength loss at every 25 freeze-thaw circulations. All experiments
were performed on three specimen replicates. The average values were used for the

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discussion of the test results.
The following Eq. (1) was used to calculate the weight loss:

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Wn  (W0  Wn ) / W0  100 (1)

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where ΔWn is the weight loss of specimens at every 25 freeze-thaw cycles (%), W0 is

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the average weight of concrete specimens before freeze-thaw cycles (kg) and Wn is
the average weight of concrete specimens at every 25 freeze-thaw cycles in water or
in the sulfate solutions (kg).

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The dynamic modulus of elasticity (DME), which was determined by Eq. (2),
was measured with a high-accuracy nonmetal ultrasonic analyzer as the initial value.
The RDME, which was determined by Eq. (3), is the ratio of DME value to the initial
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DME value after every 25 freeze-thaw cycles.
(1   )(1  2 ) V 2
Ed  (2)
1 
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Edn Vn2
RDME   (3)
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Ed0 V02

where Ed is the DME, V is ultrasonic speed (m/s), ρ is density of specimen (kg/m3)

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and υ is Poisson’s ratio, Ed0 is the dynamic modulus of elasticity of concrete

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specimens before freeze-thaw cycles (GPa), Edn is the dynamic modulus of elasticity
of concrete specimens at every 25 freeze-thaw cycles (GPa), V0 is the ultrasonic speed
of concrete specimens before freeze-thaw cycles (m/s), Vn is the ultrasonic speed of
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concrete specimens at every 25 freeze-thaw cycles (m/s).

The measurement of compressive strength property was conducted according to
the GB/T50081 (2002) method. The following Eq. (4) was used to calculate the
compressive strength:
fcc  F / A (4)
where fcc is the compressive strength (MPa), F is the maximum load (N) and A is the
area of the cube loading face (mm2).
According to the test procedure, the deterioration of the specimens was
investigated by determining the RDME loss, weight loss and compressive strength
loss. The specimen was considered to be a failure if the RDME dropped to 60%, the
weight loss exceeded 5% or the compressive strength dropped to 75%.

2.3.2. Analytical techniques

The deteriorated surfaces of selected samples were examined by scanning

electron microscopy (SEM) and equipped with an energy dispersive spectroscopy
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(EDS) detector. In addition, X-ray diffraction (XRD) (Cu-Kα) was performed on

samples to identify any compounds formed during the exposure to sulfate solutions.
Finally, thermal analysis including thermogravimetric analysis (TGA) and differential
scanning calorimetry (DSC) was conducted on powder samples collected from the
surface (0 mm to 5 mm depth from the exposed surface) of selected specimens to

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analyze the corrosion products.

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3. Results and discussion

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3.1. Surface damage

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Fig. 1 shows examples of the surface deterioration of concrete subjected to 300
freeze-thaw cycles in water and in sulfate solutions. The degree of surface
deterioration is obviously different in the three types of solutions. Concrete specimen

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exposed to the sodium sulfate solution exhibits slight attack with only a surface layer
of mortar scaled. While the specimen in water suffers loss of surface material from the
corners and edges, the surface becomes uneven, which shows that the damage is
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worse than that in the sodium sulfate solution. The coarse aggregate exposed in some
severely scaled specimens immersed in the magnesium sulfate solution even peeled
off. Visual inspection revealed that the specimen exposed to magnesium sulfate
solution is more severely damaged than that exposed to other solutions. The results
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corroborate the findings of other researchers (Rasheeduzzafar et al., 1994; Al-Amoudi

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et al., 1995). However, these studies have been conducted on cement paste or mortar
without considering the action of freezing-thaw damage.
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----Insert Fig.1----
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Fig.1. Surface damage of concrete subjected to 300 freeze-thaw cycles in water and in sulfate solutions.

3.2. Weight loss

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As shown in Fig. 2, the weight loss of concrete specimens exposed to the

magnesium sulfate solution exhibits three distinct stages. In Stage I, from the initial
immersion to 100 freeze-thaw cycles, the weight loss increases gradually. In Stage II,
from 100 to 150 freeze-thaw cycles, the weight loss decreases gradually. In Stage III,
from 150 to 400 freeze-thaw cycles, the weight loss increases from 0.32% to 1.69%.
The weight loss of concrete specimens exposed in the sodium sulfate solution also
shows a similar trend. The reason that Stage II occurs is that sulfate solution chemical
reaction leads to the formation of ettringite and gypsum, increasing the weight of
concrete to a certain extent. However, sulfate attack accelerates the formation of
microcracks in concrete under freeze-thaw cycles, which increases the ingress of
sulfate ions into concrete to a certain extent and leads to more serious deterioration in
Stage III.
The deterioration because of magnesium sulfate covers more aggressive
corrosion on concrete. Firstly, the Ca ion in the calcium silicate hydrate (C-S-H) can
be replaced by the Mg ion, leading to the formation of non-cementitious magnesium
silicate hydrate (M-S-H) and the loss of the cementitious structure (Shi et al. 2011).
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Secondly, the formation of ettringite and gypsum due to the sulfate ion cause
expansion and cracks and thus significantly lead to the deterioration of concrete.
Because of the simultaneous significant decomposition of the C-S-H that accompanies
the formation of ettringite and gypsum, the corrosive action of magnesium sulfate is
greater than that of sodium sulfate. Therefore, the weight loss of concrete in the

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magnesium sulfate solution is larger than that in water and in sodium sulfate solution
exposed to freeze-thaw cycles. The results agree with those suggested by Miao et al.

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(2001) and Mu et al. (2001). However, the results disagree with those reported by
Zhang et al. (2011), which showed that the weight loss of the HSC with a higher

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water binder ratio and a lower content of mineral admixtures in the magnesium sulfate

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solution is less than that in water.
Sulfate solution has both positive and negative effects on the concrete subjected
to freeze-thaw cycles. The positive effect is that sulfate solution permeates into the

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pores and the concentration of pore solution increases, which causes the freezing
point of pore solution to drop (Mu et al., 2001). The effect of lowering freezing point
results in concrete damaged lightly when exposed to freeze-thaw cycles. The negative
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effect is that sulfate attack results in more severe damage in concrete as freeze-thaw
cycles increase. Obviously, the positive effect is dominant when concrete is exposed
to the sodium sulfate solution, which leads to a more moderate degradation than that
in water. On the contrary, the negative effect is dominant in the magnesium sulfate
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solution.
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----Insert Fig.2----
Fig.2. Weight loss in concrete subjected to freeze-thaw cycles in water and in sulfate solutions.
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3.3. Relative dynamic modulus of elasticity loss

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As shown in Fig. 3, the RDME loss of concrete specimens in the sodium sulfate
and magnesium sulfate solutions exhibit the following three stages: (I) decreased
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stage, from the initial immersion to 75 freeze-thaw cycles, (II) slowly decreased stage,
from 75 to 200 freeze-thaw cycles and (III) accelerating decreased stage, from 200 to
400 freeze-thaw cycles. Corrosion products modify the microstructure of concrete
because of their expansion, thus the RDME loss is reduced in Stage II. However,
sulfate attack results in the formation of more microcracks in concrete during later
freeze-thaw cycles, which accelerates the RDME loss in Stage III. The experimental
results show that the RDME loss of concrete in the magnesium sulfate solution is
larger than that in water and in sodium sulfate solution. The results agree with the
weight loss presented in Fig. 2. Obviously, the positive effect is dominant in the
sodium sulfate solution during the initial 300 freeze-thaw cycles, and the decline in
the RDME loss of concrete is slower than that in water. As sulfate attack occurs
continuously, the RDME loss of concrete exposed to the sodium sulfate solution is
greater in further freeze-thaw cycles.
----Insert Fig.3----
Fig.3. RDME loss in concrete subjected to freeze-thaw cycles in water and in sulfate solutions.

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3.4. Compressive strength loss

The extent of reduction in compressive strength is greatest in the magnesium

sulfate solution, as shown in Fig. 4. After 400 freeze-thaw cycles, the compressive
strength loss ratios of concrete in 5% sodium sulfate solution, 5% magnesium sulfate
solution and water are 21.53%, 26.62% and 19.91%, respectively. As illustrated in Fig.

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4, the compressive strength loss of concrete in the two sulfate solutions exhibit the

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following three periods: (I) decreased period, (II) steady period and (III) accelerating
decreased period. The compressive strength loss of concrete tested in water is greater

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than that of concrete tested in the sodium sulfate solution in the first 250 freeze-thaw

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cycles. The damage rate of concrete in the sodium sulfate solution has been greatly
accelerated after 100 freeze-thaw cycles, and the compressive strength loss is greater
than that in water after 250 cycles. The results of compressive strength loss agree with

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those of RDME loss shown in Fig. 3. More importantly, both the positive and
negative effects of sulfate solution significantly affect the frost resistance of concrete.
----Insert Fig.4----
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Fig.4. Compressive strength loss in concrete subjected to freeze-thaw cycles in water and in sulfate
solutions.

3.5. Microscopic test analysis

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Figs. 5 and 6 present the microstructure observation of concrete subjected to

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freeze-thaw cycles in the magnesium sulfate solution. As shown in Fig. 5a,

needle-like crystals can be observed in the pores. The EDS technique was used to
characterise the chemical compositions of the needle crystals, and the results are
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reported in Fig. 5b. Careful observation of the EDS spectra showed that needle
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crystals consist of the elements Al, Si, S, Ca and Mg, which indicated that the needle
crystals are ettringite crystals. The presence of Mg is due to the precipitation of the
used magnesium sulfate salt or to the brucite (product of the reaction of portlandite
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with magnesium sulfate). As shown in Fig. 6a, short columnar crystals can be
observed in the pores. The EDS spectra of these crystals indicated that they are
gypsum, which detected the elements Si, S, Ca and Mg (Fig. 6b).

----Insert Fig.5----
Fig.5. Needle crystals in concrete subjected to freeze-thaw cycles exposed to magnesium sulfate
solution. (a) SEM and (b) EDS.

----Insert Fig.6----
Fig.6. Short columniation shape crystals in concrete subjected to freeze-thaw cycles exposed to
magnesium sulfate solution. (a) SEM and (b) EDS.

Fig. 7a shows the XRD patterns of tested samples exposed to the magnesium
sulfate solution subjected to freeze-thaw cycles. The degradation material was found
to consist mostly of ettringite, gypsum, portlandite, quartz, calcite and traces of brucite.
The ettringite and gypsum peaks in concrete are strong, which indicates that they are
main corrosion products. The results agree with those suggested by Jin et al. (2007).
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Portlandite most probably has reacted with magnesium sulfate to form ettringite,
gypsum and brucite, all of which are found in the degradation products. The
concentrations of gypsum and ettringite after 300 freeze-thaw cycles are higher than
those after 100 and 200 cycles. Moreover, the concentration of portlandite gradually
decreases, showing that the deterioration rate of concrete increases as freeze-thaw

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cycles increase.
Fig. 7b shows the XRD patterns of tested samples exposed to the sodium sulfate

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solution subjected to freeze-thaw cycles. Obviously, gypsum and ettringite are main
corrosion products. However, the concentrations of gypsum and ettringite in concrete

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exposed to the sodium sulfate solution are lower than that in the magnesium sulfate

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solution, indicating that the damage of concrete is more severe in the magnesium
sulfate solution.

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----Insert Fig.7----
Fig.7. XRD patterns of concrete subjected to freeze-thaw cycles in sulfate solutions. (a) magnesium
sulfate solution and (b) sodium sulfate solution (E:ettringite; G:gypsum; P:portlandite; Q:quartz; C:calcite;
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B:brucite).

Fig. 8 presents the TG/DSC curve of the degradation product of concrete

exposed to the magnesium sulfate solution subjected to freeze-thaw cycles. The DSC
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plots data from all the samples measured, displaying three typical endothermic peaks
that lie in the ranges 100 °C to 120 °C, 140 °C to 150 °C and 450 °C to 460 °C.
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Similar studies (Gao et al., 2013; Kresten et al., 1975) have reported that these three
temperature stages correspond to the dehydration and decomposition of ettringite,
dehydration and decomposition of gypsum, and decomposition of portlandite,
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respectively. Another extremely small endothermic peak at approximately 400 °C is

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attributed to the dehydroxylation of brucite. The concentrations of gypsum and

ettringite obtained from the TG/DSC curve after 200 freeze-thaw cycles are higher
than those after 100 cycles, which confirms the XRD observations.
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----Insert Fig.8----
Fig.8. TG/DSC curves of deterioration products of concrete exposed to magnesium sulfate solution
subjected to freeze-thaw cycles. (a) 100 cycles and (b) 200 cycles.

4. Conclusions
Sulfate solution has both positive and negative effects on the concrete subjected
to freeze-thaw cycles. The positive effect is that sulfate solution drops the freezing
point of concrete pore solution and restrains the sulfate attack when subjected to
freeze-thaw cycles. The negative effect is that the chemical reaction of sulfate solution
leads to the formation of expansion products, which results in the microcracks in
concrete and accelerates the damage process.
Because of the simultaneous significant dissolution of cement hydrates that
accompanies the formation of ettringite and gypsum, the deterioration by magnesium
sulfate covers the most aggressive corrosion on concrete subjected to freeze-thaw
cycles, and the negative effect is dominant. The interaction effect of the sodium
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sulfate attack and freeze-thaw cycles at the early test period is different from that at
the latter period. The compressive strength loss and the RDME loss of concrete in 5%
sodium sulfate solution was found to be less than the loss rates in water during the
initial freeze-thaw cycles because the positive effect is dominant. In further
freeze-thaw cycles, the negative effect of sulfate solution is more obvious and the

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damage of concrete is more severe. The weight loss of concrete in the sodium sulfate
solution subjected to freeze-thaw cycles is less than that in water in the entire

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experiment process. Additionally, the main corrosion products of concrete in sulfate
solutions subjected to freeze-thaw cycles were confirmed to be ettringite and gypsum.

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A small quantity of brucite still exists in the corrosion products when tested in the

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magnesium sulfate solution.

Acknowledgements

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This project was supported by the Durability and Life Forecast of Shotcrete
Tunnel Structure Fund (Chinese, No. 51278403) and supported by Program for
Changjiang Scholars and Innovative Research Team in University (IRT13089).
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References
Al-Amoudi, O.S.B., 1995. Performance of 15 reinforced concrete mixtures in
magnesium-sodium sulphate environments. Construction and Building Materials
D

9(3), 149-158.
TE

Al-Dulaijan, S.U., Maslehuddin, M., Al-Zahrani, M.M., Sharif, A.M., Shameem M.,
Ibrahim M., 2003. Sulfate resistance of plain and blended cements exposed to
varying concentrations of sodium sulfate. Cement and Concrete Composites 25,
P

429-437.
CE

Bassuoni, M.T., Nehdi, M.L., 2009a. Durability of self-consolidating concrete to

different exposure regimes of sodium sulfate attack. Materials and Structures
42(8), 1039-1057.
AC

Bassuoni, M.T., Nehdi, M.L., 2009b. Durability of self-consolidating concrete to

sulfate attack under combined cyclic environments and flexural loading. Cement
and Concrete Research 39(3), 206-226.
Chen, X.B., Tang, M.X., Ma, K.L., 2012. Underground concrete structure exposure
to sulfate and chloride invading environment. Journal of Central South University
(Science and Technology) 43(7), 2803-2812.
Gao, R.D., Li, Q.B., Zhao, S.B., 2013. Concrete deterioration mechanisms under
combined sulfate attack and flexural loading. Journal of Materials in Civil
Engineering 25(1), 39-44.
GB/T 50081 2002. Standard for test method of mechanical properties on ordinary
concrete. Chinese standard Institution.
GB/T 50082 2009. Standard for test method of long-term performance and durability
of ordinary concrete. Chinese standard Institution.
Jin, Z.Q., Sun, W., Jiang, J.Y., Zhao, T.J., 2008. Damage of concrete attacked by
sulfate and sustained loading. Journal of Southeast University 24(1), 69-73.
Jin, Z.Q., Sun, W., Zhang, Y.S., Jiang, J.Y., Lai, J.Z., 2007. Interaction between sulfate
9
 ACCEPTED MANUSCRIPT

and chloride solution attack of concretes with and without fly ash. Cement and
Concrete Research 37(8), 1223-1232.
Kresten, P., Berggren, G., 1975. The thermal decomposition of thaumasite.
Thermochim Acta 20(6), 1-6.
Liu, L.X., 2001. Brief introduction on the study of erosion and prevention of concrete

T
in salt lake and saline soil area of Chaerhan, Chadamu, Journal of Building
Materials 4(4), 395-400.

IP
Mehta, P.K., 1991. Concrete Durability-Fifty Years Progress. Progress of 2nd
international Conference on Concrete Durability. ACI SP 126-11-31.

R
Miao, C.W., Mu, R., Tian, Q., Sun, W., 2001. Effect of sulfate solution on the frost

SC
resistance of concrete with and without steel fiber reinforcement. Cement and
Concrete Research 32(1), 31-34.
Mu, R., Miao, C.W., Liu, J.P., Sun, W., 2001. Effect of NaCl and Na2SO4 solution on

NU
the frost resistance of concrete and its mechanism. Journal of the Chinese Ceramic
Society 29(6), 523-529.
Ramyar, K., İnan, G., 2007. Sodium sulfate attack on plain and blended cements.
MA
Building and Environment 42(3), 1368-1372.
Rasheeduzzafar, Al-Amoudi O.S.B., Abduljauwad, S.N., Maslehuddin, M., 1994.
Mechanisms of magnesium-sodium sulfate attack in plain and blended cements.
Journal of Materials in Civil Engineering 6(2), 201-222.
D

Shanahan, N., Zayed, A., 2007. Cement composition and sulfate attack Part I. Cement
TE

and Concrete Research 37(4), 618-623.

Shi, X.M., Fay, L., M. Peterson, M., Berry, M., Moony, M., 2011. A FESEM/EDX
investigation into how continuous deicer exposure affects the chemistry of
P

Portland cement concrete. Construction and Building Materials 25(2), 957-966.

CE

Skalny, J., Marchand, J., Odler, I., 2002. Sulfate Attack on Concrete, Spon Press, UK.
Wang, Y.L., Yao, Y., 2001. Researches on key engineering concrete durability and
applications. China Building Material, Beijing.
AC

Wee, T.H., Suyavanshi, A.K., Wong, S.F., Rahman, A.K.M.A., 2000. Sulfate
resistance of concrete containing mineral admixtures. Journal of Materials in Civil
Engineering 97, 536-549.
Yu, H.F., Mu, R., Sun, W., Miao, C.W., 2005. Effects of flexural loads, chemical
attack, carbonation and their combination on freezing-thawing durability of
concretes. Journal of the Chinese Ceramic Society 33(4), 492-499.
Yu, H.F.，Sun, W., Zhang, Y.S., Guo, L.P., Li, M.D., 2008. Durability of concrete
subjected to the combined actions of flexural stress, freeze-thaw cycles and bittern
solutions. Journal of Wuhan University Technology Materials Science 23(6),
893-900.
Zhang, Y.Q., Yu, H.F., Sun, W., Zhang, J.Y., 2011. Frost resistance of concrete under
action of magnesium sulfate attack. Journal of Building Materials 14(5), 698-702.
Zheng, X.N., Diao, B., Sun, Y., Zhang, W.M., 2010. Study of deterioration mechanism
of concrete in multiaggressive and freeze-thaw environment. Journal of Building
Structures 31(2), 111-116.

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1. Fig.1. Surface damage of concrete subjected to 300 freeze-thaw cycles in water and in sulfate

solutions.

2. Fig.2. Weight loss in concrete subjected to freeze-thaw cycles in water and in sulfate solutions.

3. Fig.3. RDME loss in concrete subjected to freeze-thaw cycles in water and in sulfate solutions.

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4. Fig.4. Compressive strength loss in concrete subjected to freeze-thaw cycles in water and in

sulfate solutions.

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5. Fig.5(a). SEM of needle crystals in concrete subjected to 200 freeze-thaw cycles exposed to

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magnesium sulfate solution.

6. Fig.5(b). EDS of needle crystals in concrete subjected to 200 freeze-thaw cycles exposed to

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magnesium sulfate solution.

7. Fig.6(a). SEM of Short columniation shape crystal in concrete subjected to 200 freeze-thaw cycles
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exposed to magnesium sulfate solution.

8. Fig.6(b). EDS of Short columniation shape crystal in concrete subjected to 200 freeze-thaw cycles
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exposed to magnesium sulfate solution.

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9. Fig.7(a). XRD patterns of concrete subjected to freeze-thaw cycles in magnesium sulfate solution.

10. Fig.7(b). XRD patterns of concrete subjected to freeze-thaw cycles in sodium sulfate solution.
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11. Fig.8(a). TG/DSC curves of deterioration products of concrete exposed to magnesium sulfate
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solution subjected to 100 freeze-thaw cycles.

12. Fig.8(b). TG/DSC curves of deterioration products of concrete exposed to magnesium sulfate
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solution subjected to 200 freeze-thaw cycles.

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Fig 1

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Fig 2
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Fig 3
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Fig 4
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Fig 5a
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Fig 5b
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Fig 6a
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Fig 6b
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Fig 7a
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Fig 7b
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Fig 8a
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Fig 8b
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13. Table 1 Chemical composition of OPC and fly ash.

14. Table 2 Mix proportion and compressive strength of concrete.

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Table 1
Chemical composition of OPC and fly ash.
Constituent (wt.%) SiO2 Al2O3 CaO MgO SO3 Fe2O3 Na2O K2O Loss

OPC 21.66 5.13 64.37 1.06 2.03 5.25 0.25 1.35 4.12
Fly ash 49.02 31.56 4.88 0.83 1.2 6.97 0.43 1.36 3.65

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Table 2
Mix proportion and compressive strength of concrete.
Water-binder Cement Fly ash Water Aggregate Sand Superplas Air Compressive
-3 -3 -3 -3 -3
ratio /(kg·m ) /(kg·m ) /(kg·m ) /(kg·m ) /(kg·m ) -ticizer content /% strength/MPa
/% 28d 90d

0.45 285 70 160 1300 585 0.5 4.2 32.3 43.2

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Highlights
15. Properties of concrete under freeze-thaw and sulfate conditions have been studied.

16. Different types of sulfate solutions have been selected.

17. The microstructure of concrete has been investigated.

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18. Frost resistance of concrete is dependent on the types of sulfate solutions.

19. There is an interaction effect between sulfate attack and freeze-thaw cycles.

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