Construction and Building Materials 293 (2021) 123550

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Compressive strength assessment of sulfate-attacked concrete by using

sulfate ions distributions
Hanbin Cheng, Tiejun Liu, Dujian Zou ⇑, Ao Zhou
School of Civil and Environmental Engineering, Harbin Institute of Technology, Shenzhen 518055, PR China

h i g h l i g h t s

The performance of concrete under sulfate attack and dry-wet cycles is investigated.

A newly defined index is proposed to describe the progress of sulfate attack.

A novel method is proposed to assess the performance of sulfate-attacked concrete.

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

Article history: Sulfate attack is a major cause of concrete durability deteriorations. Mass loss, strength reductions, and
Received 28 January 2021 expansive strain of concrete specimens are generally used in laboratory testing to identify the resistance
Received in revised form 9 April 2021 of concrete materials to sulfate attack. However, these indicators cannot be directly used to quantita-
Accepted 30 April 2021
tively predict the bearing capacity of actual concrete structures under sulfate attack. There exists a sig-
Available online 10 May 2021
nificant size effect between laboratory and engineering size concrete components. In this study, the
durability performance of concrete specimens, exposed to sulfate attack and dry–wet cycles, was inves-
Keywords:
tigated. Mass loss, dynamic elastic modulus, compressive strength, and sulfate ions distributions of dete-
Concrete material
Sulfate attack
riorated concrete were measured over time. Test results indicate that the newly defined integral area of
Non-uniform deteriorations sulfate ions distributions is a suitable index to describe the non-uniform deteriorations behavior of sul-
Homogenization’s theory fate–attacked concrete; and a novel method based on the homogenizations theory is proposed to predict
Sulfate ions distributions the deteriorations level of components of attacked concrete structures, which provides a potential use in
Strength assessment assessing the loading capacity of actual concrete structures based on accelerated test results in a
laboratory.
Ó 2021 Elsevier Ltd. All rights reserved.

1. Introductions
Sulfate attack is a major contributing factor to the deteriora-
tions of cement-based materials [1–5]. Sulfates are naturally
occurring minerals found in saline-alkali soil, groundwater, and
coastal areas [6]. Considering the actual exposure environment,
sulfate ions are not always the only erosion chemical products,
degradations process induced by sulfate attack usually can be
accelerated by other ions, including chlorides [7,8] or magnesium
[9]. The deteriorations of concrete structures exposed to sulfates
is caused by the formations of ettringite and gypsum resulting
from the chemical reactions of sulfate ions and cement hydrate
products [10–12]. Two typical manifestations of sulfate attack on
concrete structures are the disruptive expansive cracks and mass
⇑ Corresponding author.
E-mail addresses: chenghanbin1994@gmail.com (H. Cheng), liutiejun@hit.edu.cn
(T. Liu), zoudujian@163.com (D. Zou), zhouao@hit.edu.cn (A. Zhou).
loss that occur [13–24]. Therefore, mass loss and expansive strain
are generally recommended as measuring indices by current codes
to assess the deteriorations level of sulfate-attacked concrete in
laboratory testing [25,26]. Based on the systematic study on the
change of mesoscopic pore structures induced by chemical sulfate
attack and physical sulfate attack, pore structures can also express
the degradations process of sulfate attack inside concrete [27,28].
Furthermore, according to the analysis of phase compositions of
corrosions products, the damage level of sulfate attacked concrete
could also be revealed by using XRD and SEM-EDS [13–17]. In addi-
tions, depth of sulfate attack could also be used as the indicator to
express the deteriorations of concrete under the attack of sulfate
[13–18]. Although the above discussed indicators and methods
are straightforward and reliable in identifying the resistance of dif-
ferent concrete materials exposed to sulfate attack, the compres-
sive strength of sulfate attacked concrete is one of the important
points of concern [29].

https://doi.org/10.1016/j.conbuildmat.2021.123550
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
H. Cheng, T. Liu, D. Zou et al.
The mechanical property or constitutive relations of deterio-
rated concrete is critically important to assess the safety of con-
crete structures in aggressive environments. Many experimental
investigations have been reported in the study of the compressive
strength and flexure strength of sulfate-attacked concrete [4,30–
39]. Meanwhile, recent studies focus on using or dynamic elastic
modulus [29] or static elastic modulus [40] to conduct assessment
on sulfate attacked. Considering many actual structures bearing
shear stress, other experimental investigation uses shear strength
as the main indicator to express damage level of sulfate-attacked
concrete [41]. However, these tests primarily focus on the acceler-
ated deteriorated tests using small-scale concrete specimens.
However, as to sulfate attacked concrete, the deteriorations is not
uniform across the sections area of concrete. The exterior part of
concrete may be severely deteriorated while the inner part of con-
crete could remain healthy [42–47]. Therefore, the isotropy
assumptions, that generally employed to study the constitutive
relations of normal concrete, cannot be applied to the analysis of
concrete under sulfate attack in actual conditions [48,49]. In addi-
tions, the size effect between concrete specimens of various sizes
under the same environmental conditions is not fully investigated
[29]. For the identical deterioration depth of concrete, the decrease
in bearing capacity of concrete members varies between the tested
size and engineering size of concrete members. Based on the above
discussions, the accelerated test results cannot be used to predict
the damage level of full-scale concrete members in actual
conditions.
Considering the existing research, it is a prerequisite to propose
a new indicator and method to predict and assess strength of sul-
fate attacked concrete. In this study, based on the homogeniza-
tion’s theory, the attacked concrete was considered to be divided
into two sections, namely the damaged area and healthy area.
The strength of healthy area of concrete was assumed to be equal
to that of normal concrete. Therefore, the key to strength assess-
ment of sulfate attacked concrete lies on the strength predictions
of attacked area of concrete. Based on experimental results, the
sulfate ions distribution was used to identify the attacked area
and the integral areas of sulfate ions distributions at various times
were calculated to express the deteriorations process of concrete
under sulfate attack. Then, a preliminary relationship between
the integral area of sulfate ions distributions and the compressive
strength of attacked area of concrete was established by using
robust regressions analysis. Finally, a novel methodology based
on homogenizations and sulfate ions distributions was proposed
to assess the compressive strength of attacked concrete members.
2. Experimental investigations
2.1. Materials and concrete specimens
The 42.5R ordinary Portland cement of Guangdong Huarun
Cement (Fengkai) Co., Ltd. was used in this test. It has a specific
surface area of 362 m2/kg, and its stability is qualified. The detailed
chemical compositions are listed in the Table. 1.
The fly ash used in the test is the product of Shajiao C Power
Plant of Guangdong Yuedian Group Co. Ltd. The fineness of fly
ash is 21.30. The water demand ratio is 99% and the ignition loss
is 1.64%. The fine aggregate used in this test is river sand produced
in Dongguan. Apparent density is 2570 kg/m3, bulk density is
Table.1
Cement compositions.
Composition Na2O MgO Al2O3
Content (%) 0.46 0.86 4.99
2
Construction and Building Materials 293 (2021) 123550
1470 kg/m3, fineness modulus is 2.7, silt content is 0.8%. Coarse
aggregate comes from Huizhou, with needle-like content of 2.0%,
crushing index of 8.0%, silt content of 0.5%, and maximum particle
size of 25 mm. STD-1 retarding superplasticizer was used in this
experiment.
Commercial concrete, supplied by Shenzhen Tiandi Concrete
Corporations, was used for testing in this study. Three water–bin-
der ratios (W/Bs) of concrete were considered, and the detailed mix
proportions are presented in Table 2. Sulfate solutions with mass
fractions of 3%, 5%, and 10% were used to accelerate the deteriora-
tions process of concrete. A total of 288 concrete specimens were
cast (Table 3) and 45 of these concrete specimens were prepared
for the control test curing in water. All concrete specimens were
cured for 28 days in a standard environment with a temperature
of 20 °C and relative humidity of 95%.
2.2. Deteriorations of concrete specimens
Two-dimensional sulfate attack was considered in the test. The
top and bottom surfaces of all concrete specimens were sealed
with paraffin as illustrated in Fig. 1. Concrete specimens were first
fully immersed in the sulfate solutions at room temperature for
seven days and dried at room temperature for eight days, which
represents a dry–wet cycle. When the concrete specimens were
fully immersed in the sulfate solutions, the pools were covered
with plastic film to prevent volatilizations of sulfate solutions,
and the solutions was replaced every month.
2.3. Test devices and methods
2.3.1. Mass loss
All concrete specimens for each mixture were transferred to the
exposure conditions after measuring their initial mass by using a
balance with an accuracy of 0.1 g. Considering the influence of
water content inside concrete, all concrete specimens were dried
at lab room temperature until mass reached to stable state before
being measured initial mass. Except for the control concrete spec-
imens, all the concrete specimens were immersed in a sulfate solu-
tion for seven days and dried at room temperature for eight days
until a constant mass was reached, which constitutes one cycle
of sulfate attack. After each cycle, the mass for each concrete spec-
imen was measured. The specific measuring method followed the
standards outlined in GB/T50082-2012 [26], and the mass loss
ratio was calculated according to Eq. (1):
Wt  W0
DW t ¼ 100  ð1Þ
W0
where DWt represents the mass change fractions, W0 indicates the
initial mass of the concrete specimen, and Wt represents the mass
of the concrete specimen at the deteriorations time of t.
2.3.2. Mechanical tests
The dynamic elastic modulus was determined by using a
dynamic elastic modulus measurement machine (Model DT-
20W) was the setup. The measuring method followed the standard
test method of mechanical properties for ordinary concrete [49].
The relative dynamic elastic modulus (RDEM) was used to evaluate
the compactness of the concrete specimens under sulfate attack,
and it was calculated by:
SiO2 SO3 K2O CaO Fe2O3
26.01 0.55 0.48 65.78 2.49
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Table.2
Concrete Mix Proportions.

Strength grade Slump (mm) W/C Coarse aggregate (kg/m3) Sand (kg/m3) Cement (kg/m3) Fly ash (kg/m3) Water reducing agent (%) Water (kg/m3)
C20 140–180 0.57 1030 870 190 80 2.75 167
C30 140–180 0.47 1040 815 260 80 2.80 166
C45 140–200 0.37 1050 740 345 80 2.90 159

Table.3
Deteriorations Groups of Specimens.

Exposure conditions W/C Concentrations (%) Prism 1 Prism 2 Compressive strength at 28 days (MPa)
Na2SO4 0.37 3% 23 4 38.803
5% 23 4
10% 23 4
0.47 3% 23 4 23.021
5% 23 4
10% 23 4
0.57 3% 23 4 14.039
5% 23 4
10% 23 4
H2O 0.37 – 15 0 38.803
0.47 – 15 0 23.021
0.57 – 15 0 14.039

Note: Prism 1: 150 mm  150 mm  300 mm; Prism 2: 100 mm  100 mm  400 mm

Fig. 1. Sulfate attack test.

Erd ðtÞ ¼ Ed ðtÞ=Ed ð0Þ ð2Þ

where Erd(t) represents the RDEM of concrete specimens after t
days of sulfate attack; Ed(t) denotes the dynamic elastic modulus
of concrete specimens after t days of sulfate attack; and Ed(0) indi-
cates the initial dynamic elastic modulus of concrete specimens.
A servo-hydraulic testing machine with a capacity of 5000 kN
(YAS-5000) was used to conduct the compressive testing. The dis-
placement loading method was employed at a rate of 0.01 mm/s.
The detailed testing method followed the GB 50081-2019
guidelines.

2.3.3. Determinations of sulfate ions distributions

The distribution of sulfate ions at different depths in concrete
were determined using core samples of concrete specimens as
depicted in Fig. 2 at various periods of 60, 120, 180, 240, and
300 days. The sampling depth was set to 20 mm, and the corre-
sponding thickness for each slice was 2 mm. In this test, a precision
cutting machine was used to cut the concrete slices. During the
process, water is needed to cool down the machine, in order to
avoid sulfates dissolved and leached away, limited amount of
water was carefully sprayed on the blade to cool down every 2–
Fig. 2. Concrete core.
3 min. Besides, 25 pieces of diamond cutting blade were prepared
for blade replacement. The concrete slices were first dried in a dry-
ing oven at the temperature of 40 °C for 24 h and then crushed in a
ceramic mortar. The larger particles, including sand or stones, were
removed, and the remaining particles were ground repeatedly until
all the particles could pass through a sieve with a diameter of
0.045 mm.

3
H. Cheng, T. Liu, D. Zou et al.
The sulfate ions content in each layer of the four core samples of
concrete powder was determined by chemical analysis based on
ASTM C114-15 [50]. The steps for this analysis are presented in
detail in Fig. 3. First, the weighed concrete powder was dissolved
in hydrochloric acid; then, barium chloride was added to the solu-
tions to obtain barium sulfate precipitations. The suctions filtering
machine was used to obtain the barium sulfate precipitations from
the mixture solutions. The mean value of the four measurements
was taken as the sulfate ions content of each layer. However, the
value, exceeding 15% of the mean value, was invalid. The percent-
age of sulfate ions content at different depths of attacked concrete
can be calculated according to Eq. (3):
0:412  ðm3  m2 Þ
w¼
m1
where w represents the percentage of SO2-
4 content (%); 0.412 indi-
cates the conversions coefficient factor of the relative molecular
mass between barium sulfate and sulfate tetraoxide; m3 represents
the total mass of barium sulfate and filter membrane; m2 denotes
the mass of filter membrane; and m1 represents the mass of con-
crete powder.
3. Results and discussions
3.1. Mass loss
Fig. 5 illustrates the development of mass loss with sulfate
attack time. According to Fig. 5a and b, the mass loss for concrete
with W/B of 0.37 and 0.47 consists of three main stages, including
a rapidly rising stage, a slow rising stage, and a falling stage. During
the first stage, there are three main reasons for the rapid increase
of the mass of concrete specimens: (1) the further hydrations of
cement; (2) the new generations of sulfate attack reactions prod-
Fig. 3. Sulfate ions titrations experiment.
Construction and Building Materials 293 (2021) 123550
ucts, namely gypsum and ettringite; and (3) the depositions of sul-
fate salt crystals resulting from water evaporations during the dry–
wet cycle. In the second stage, the cement hydration is completed,
and the mass increase is attributed to the continuations of sulfate
attack and depositions of sulfate salt crystals. When there are too
excessive deposited expansive products concentrating in concrete
initial pores and cracks, a tension develops which is greater than
the tensile strength of the concrete material. Under this condition
in the experiment, new cracks were generated, and the scaling and
peeling of cement produced a decrease in the mass of the concrete
specimens. However, for the concrete with a larger W/B (0.57), the
mass loss occurred in a two-stage change, namely a rapidly
increasing period followed by a falling period. This difference
stems from the rapid diffusions of sulfate ions caused by the larger
ð3Þ
W/B. During the first stage for the concrete with a larger W/B
(0.57), the increase in mass was also attributed to further cement
hydrations. Also, a large amount of ettringite and sulfate salt crys-
tal was already deposited in the initial pores or cracks of the con-
crete, shown in the Fig. 4. With further development of expansive
products and more deposited salt crystal, there was a rapid forma-
tion of cracks leading to spalling and peeling off, and the mass loss
reached the falling stage. [51] It can be concluded that a larger W/B
can cause a greater mass change at both the increasing and falling
stages. Because a larger W/B provide more pathways for sulfate
ions diffusions.
Another influential factor during the sulfate attack process is
the concentrations of the sulfate solutions. Under general condi-
tions, a larger concentrations of sulfate solutions could promote
the diffusions of sulfate ions into the concrete specimens. How-
ever, during the dry–wet cycle, more sulfate crystals could be
formed when the solutions evaporate. The combined influence of
more generated chemical products and deposited salt crystals
accelerates the process of sulfate attack in terms of chemical and
4
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Fig. 4. Sulfate attack chemical products.

Fig. 5. Mass loss ratio of concrete under dry-wetting sulfate attack.

physical perspectives [51–53]. As illustrated in Fig. 5, it is interest-
ing to observe that the mass increase at the early stage is not
always proportional to the sulfate solutions concentrations. A
higher solution concentration does not always lead to greater
weight gain at the early increasing stage. However, the descent
rate of the mass loss ratio at the falling stage is positively related
to the solutions concentrations. It can thus be concluded that a sul-
fate solution with a higher concentration can cause severe damage
to concrete specimens in the falling stage.
3.2. Dynamic elastic modulus
Fig. 6 presents the variations of the dynamic elastic modulus for
each dry–wet cycle. For concrete with W/B of 0.37, 0.47, and 0.57,
the dynamic elastic modulus undergoes three stages: a rapidly
increasing stage, a steady stage, and a falling stage. Prior to 75 days
of exposure, cement hydrations contributed to the compactness of
the concrete. During this time, the sulfate attack was mainly con-
centrated on the surface area of the concrete. The depositions of

5
H. Cheng, T. Liu, D. Zou et al.
ettringite and gypsum caused the concrete to condense, which
increased the stiffness of the concrete. Additionally, the deposited
sulfate salt crystal during the dry–wet cycle also improved the
compactness of the sulfate-attacked concrete. Therefore, during
the first stage, the dynamic elastic modulus increased quickly.
Combined with continuously generated expansive products and
the crystallizations of sodium sulfate during the drying cycle,
micro cracks developed, and the dynamic elastic modulus began
to decrease rapidly [51–54].
As presented in Fig. 6a, the influence of solutions concentrations
on the dynamic elastic modulus is similar to the influence of solu-
tions concentrations on mass loss. At the dropping stage, the des-
cent rate of dynamic elastic modulus with higher solutions
concentrations is significantly larger than that of lower solutions
concentrations. It is also observed that the dynamic modulus of
concrete with a higher W/B began to decrease at an earlier age,
which indicates that the expansive damage caused by chemical
reactions and crystallizations first occurred in concrete with a
higher W/B.
3.3. Compressive strength
Fig. 7 presents the evolutions of the compressive strength for all
groups of concrete specimens after each testing period. The com-
pressive strength of the three groups of concrete presents a similar
Fig. 6. Dynamic elastic modulus of concrete under dry-wetting sulfate attack.
6
Construction and Building Materials 293 (2021) 123550
trend. Except for the control concrete group with a W/B of 0.37, the
compressive strength decreases from 41.90 MPa to 37.84 MPa
when the time increases from 240 days to 300 days. It can also
be observed that the compressive strength of the control concrete
increases continuously with time, while the compressive strength
of attacked concrete first increases and then decreases with time.
The inconsistent test results for the control concrete group may
be caused by the variations of raw materials or the fabrications
process of the specimens.
Based on the Fig. 7, the compressive strength of concrete spec-
imens in water is almost continuously increasing, which means
that the cement hydration is generally throughout the whole
attack test span. Therefore, as to concrete specimens under sulfate
attack, the strength change is jointly influenced by cement hydra-
tions and sulfate attack. To avoid the influence of cement hydra-
tions on compressive strength degradations and more accurately
analyze the influence of sulfate attack on compressive strength of
concrete specimens, a deteriorations factor, Kf(t), is introduced to
express the deteriorations of compressive strength. Kf(t) can be
defined as follows:
f s ðtÞ
Kf ðtÞ ¼ ð4Þ
f o ðtÞ
where Kf(t) represents the deteriorations factor of compressive
strength after t days of sulfate attack; fs(t) indicates the compres-
H. Cheng, T. Liu, D. Zou et al.
Fig. 7. Compressive strength of concrete under dry-wetting sulfate attack.
sive strength of concrete specimens under sulfate attack after t
days; and f0 denotes the compressive strength of concrete speci-
mens curing in water for t days.
The deteriorations factor is the ratio of strength of attacked con-
crete to strength at the same soaked time. As discussed before, the
strength of sulfate attacked concrete is jointly influenced by
cement hydrations and sulfate attack, so, strength of sulfate
attacked concrete could be expressed as the follow:
f s ðtÞ ¼ f 0 ðtÞ þ f sulfate ðtÞ
where, fsulfate(t) refers to the strength change contributed by sulfate
attack. And Kf(t) could be expressed as the following equations:
f 0 ðtÞ þ f sulfate ðtÞ
Kf ðtÞ ¼
f 0 ðtÞ
Therefore, when Kf(t) is larger than 1.0, it refers that fsulfate(t) is
larger than 0 Mpa, which indicates sulfate attack play a positive
influence on strength of concrete due to deposited chemical prod-
ucts. When Kf(t) is equal to 1.0, it refers that fsulfate(t) is equal to
0 MPa, which indicates a critical state that sulfate attack no longer
strengthens the compressive strength of concrete and is about to
lead strength reductions. When Kf(t) is smaller than 1.0, it refers
that fsulfate(t) is minus, which indicates that strength reduction
was resulted from sulfate attack.
Fig. 8 presents the variations of Kf(t) for all attacked concrete
specimens. Generally, the Kf(t) of attacked concrete presents a sim-
ilar change as that of compressive strength, but the turning points
Construction and Building Materials 293 (2021) 123550
of deteriorations indicated by fs(t) and Kf(t) are not consistent. For
instance, as shown in Fig. 8(a), the Kf(t) of the concrete specimen
with a W/B = 0.37 in the 10% sulfate solutions is less than 1 after
been attacked for 120 days, which indicates that sulfate attack
no longer strengthens the compressive strength of concrete but
begins to cause damage. However, as presented in Fig. 7(a), the
compressive strength of attacked concrete begins to drop after
180 days of exposure. This indicates that although the sulfate
attack began to damage the concrete after 120 days, the strength
ð5Þ
increase caused by cement hydrations was greater than the
strength decrease caused by sulfate attack until 180 days. The main
reaseon for this phenomenon is that, from 120 days to 180 days,
the strength rediction due to sulfate attack was always accumulat-
ing until the point when strength reduction is equal to the strength
ð6Þ
increase resulted from cement hydration. After this point, 180 days,
sulfate attack was intensified which leads to the strength reduction
which is larger than strength gain from cement hydration. Under
this condition, the turning point of compressive strength appeared,
the compressive strength started to decrease. As for the influence
of solutions concentrations on Kf(t), it can be clearly observed in
Fig. 8 that the variations of Kf(t) with solutions concentrations all
increase at the early stage and decrease later. The larger the solu-
tions concentrations, the greater the gain of Kf(t) at the increasing
stage, and the greater the loss of K(t) at the dropping stage. It is
noted that as to concrete specimens with W/B = 0.37, the increase
of strength and K(t) of specimens in 10% sulfate solutions is not lar-
ger than that of specimens in 3% sulfate solutions, as shown in the
7
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Fig. 8. Kf(t) of concrete under dry-wetting sulfate attack.

Fig. 7(a) and Fig. 8(a). The main reason could be attributed to that
the compressive strength of concrete in 10% sulfate solutions did
reach to peak on one day within the range from 60 days to
120 days. And the strength peak of concrete in 10% sulfate solu-
tions could be truly larger than that of concrete in 3% sulfate solu-
tions. However, the peak strength could not be measured due to
compressive strength is measured every 60 days.
Fig. 9 presents the variations of Kf(t) with different W/Bs
exposed to 10% Na2SO4 solutions after each testing period. Prior
to 60 days, the Kf(t) increases with the W/B. In general, concrete
with a higher W/B has more paths and pores connected to the
external environment. As can be observed in Fig. 9, at the same
deteriorations time, more sulfate ions diffused into the concrete
specimens and reacted with the cement to produce ettringite.
The ettringite performed a filling effect on the concrete, and an
increase in densifications introduced a larger Kf(t). It is worth not-
ing that the Kf(t) of concrete with a W/B = 0.37 first started to less
than 1, which does not indicate that concrete with a lower W/B is
Fig. 9. Kf(t) of concrete with different W/C under dry-wetting sulfate attack.
more susceptible to severe damage. The concrete with a low W/B
generally has fewer initial pores and cracks. Thus, the capacity
for the accommodations of deposited products is limited, which
concrete with a W/B = 0.47, which indicates that a larger W/B
leads to a smaller increase in compressive strength. The test results
can accelerate the sulfate attack. After 300 days, the sulfate attack
indicate that when erosions product accumulates, the new cracks
damage increased with the W/B. The W/B is the primary factor
generate quickly, which causes a decrease in Kf(t). The Kf(t) of
influencing the deteriorations progress of sulfate attack such that
concrete with a W/B of 0.57 dropped below 1 sooner than that of
a larger W/B could accelerate the progress of sulfate attack. On

8
H. Cheng, T. Liu, D. Zou et al.
the other hand, a smaller W/B could decrease the permeability of
concrete, which improves the resistance of concrete to sulfate
attack.
3.4. Distributions of sulfate ions in concrete
After removing the initial sulfate ions content, the distributions
of sulfate ions in all groups of concrete with different attack ages is
presented in Figs. 10–12. The initial sulfate ions content for con-
crete specimens with W/Bs of 0.37, 0.47, and 0.57 are 1.0%,
0.91%, and 0.73%, respectively. Fig. 10 indicates that the overall
trend of sulfate ions distributions in concrete with a W/B of 0.37
in different concentrations of sulfate solutions is similar. The closer
to the concrete surface, the greater the sulfate ions content is. The
sulfate ions content in the first layer is significantly higher than
that of the second layer, as illustrated by a sudden dropping phe-
nomenon. With the attack time, the sulfate ions content in all lay-
ers increased, indicating the progress of deterioration. Figs. 11 and
12 show the time-varying distributions of sulfate ions in concrete
with W/B of 0.47 and 0.57, respectively. The sulfate ions were con-
centrated in the first layer and decreased as the depth increased at
the early ages from 60 days to 180 days, as observed in Fig. 10. As
the sulfate attack progressed, the sulfate ions content in each layer
of concrete increased. However, after 240 days, the sulfate ions
content in the first layer dropped and became concentrated in
the second layer rather than the first layer. This phenomenon is
quite different from the distribution’s behaviors shown in the
Fig. 10. The main reason for the changing behavior of sulfate ions
Fig. 10. Sulfate ions distributions of concrete with w/b = 0.37.
9
Construction and Building Materials 293 (2021) 123550
in the first layer is due to the formations of peak concentrations
of sulfate ions. The peak concentrations of sulfate ions may be
attributed to the precipitations of solid sulfates at a certain depth
such as ettringite and gypsum formed by the chemical reactions
between the hydrates and penetrating sulfate ions. By increasing
the immersions time, more sulfate ions penetrate the concrete,
and the penetrations depth increases with the diffusions process.
Meanwhile, the peak concentrations of sulfate ions increases and
shifts to greater depths [55,56]. As to concrete specimens with a
lower water-binder ratio, the sulfate attack progress is hindered
by the denser and more compact concrete matrix, the ions peak
concentrations layer hardly penetrates the concrete inner part,
only located at the first layer.
Table 4 lists the attack depths of all groups of concrete speci-
mens. The sulfate attack depth is defined as the point where sulfate
ions concentrations is 0%. It is generally shown that the attack
depth of all attacked concrete gradually increases with deteriora-
tions progress. However, further analysis indicates that there are
several limitations of using sulfate attack depth as the main indica-
tor of sulfate–attacked concrete.
First, the attack depth based on experimental results can only
roughly describe the progress of sulfate attack. For instance, the
attack depth of concrete with a W/B of 0.47 in the 5% Na2SO4 solu-
tions does not increase from 120 days to 180 days. Whereas, at the
same time, the sulfate attack deteriorations continuously progress.
Moreover, sulfate attack depth cannot identify the influence of
different factors on sulfate attack deteriorations. For instance, after
240 days of exposure, the same attack depth was detected in the
H. Cheng, T. Liu, D. Zou et al.
Fig. 11. Sulfate ions distributions of concrete with w/b = 0.47.
concrete specimens with a W/B of 0.57 in both 5% and 10% Na2SO4.
However, the deteriorations rate of these two groups of concrete
specimens is different. The compressive strengths of concrete spec-
imens in 5% and 10% sulfate solutions are 21.18 MPa and 19.4 MPa,
respectively, and the mass loss ratios for these two groups of con-
crete specimens are 0.75% and 0.62%. Furthermore, the dynamic
elastic modulus is 36.61 GPa and 35.83 GPa. Therefore, although
equal sulfate attack depths are detected in these two conditions
of concrete, the deterioration of specimens in 10% sulfate solutions
is more serious.
Finally, another limitation of sulfate depth is that aggregates
could interfere the diffusions of sulfate ions. Merely based on sul-
fate attack depth, the damage level of sulfate-attacked concrete
could not be revealed. For instance, after 300 days of exposure,
for concrete specimens with a W/B of 0.57 in both 5% and 10% sul-
fate solutions, the depth for specimens in 5% sulfate solutions is
19 mm, whereas the depth for concrete in 10% sulfate solutions
is 17 mm. However, the deteriorations of concrete in 10% sulfate
solutions is more severe. The compressive strength for these two
groups of concrete is 17.8 MPa and 17.1 MPa, respectively. The
mass loss ratios are 0.04% and 0.23%, and the dynamic elastic
moduli are 32.88 GPa and 31.85 GPa, respectively. The same situ-
ations can also be found in the concrete specimens with a W/B of
0.37 in 3% and 5% Na2SO4 after 240 days of sulfate attack.
Based on the above discussions, by only using the sulfate attack
depth, the deteriorations process cannot be fully expressed, and
the influence of various factors on the sulfate–attack process can-
not be identified. To conduct further quantitative analysis, the inte-
gral area of sulfate ions distributions is introduced. The integral
area of sulfate ions is defined as the area enclosed by the sulfate
10
Construction and Building Materials 293 (2021) 123550
ions distributions curve, mass ratio, and depth axes as illustrated
in Fig. 13. Table 5 presents the integral area of all attacked concrete
with soak time. The integral area increases with the attack time. At
the same deteriorations period, the integral area increases monoto-
nously with the W/B and sulfate solutions concentrations. There-
fore, the integral area of sulfate ions distributions can more
specifically describe the progress of sulfate attack.
The time-varying model of the integral area of sulfate ions has
been established by using multivariate fitting functions in Origi-
nLab Pro 9.1. The test data was fitted to formulate the following
equations:
4:345
SðtÞ ¼ ð0:882  1:177  w=bÞ  1:371  ðw=bÞ
ð1:544 þ 10:912  scÞ  ð93:913 þ 1:497  tÞ ðR  S ¼ 0:91Þ
ð7Þ
where S(t) represents the integral area of sulfate ions distributions
after t days of sulfate attack; w/b represents the W/B of the concrete
specimen; and sc indicates the concentrations of external sulfate
solutions.
4. Deterioration analysis of the damaged area of concrete
4.1. Definitions and basic assumptions of the damaged area
The deteriorations level is not uniformly distributed in the
sulfate-attacked concrete. Generally, the deterioration begins at
the surface and diminishes as depth increases. For simplifications,
the cross–section of attacked concrete is divided into a deterio-
rated area and a healthy area as presented in Fig. 14. The load bear-
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Fig. 12. Sulfate ions distributions of concrete with w/b = 0.57.

Table 4
The depth of sulfate attack (mm).

W/C Concentrations (%) 60 d 120 d 180 d 240 d 300 d

0.37 3% 3 7 9 13 15
5% 3 7 9 11 19
10% 5 11 13 19 19
0.47 3% 7 9 11 11 17
5% 11 13 13 17 17
10% 13 13 15 17 17
0.57 3% 13 13 13 17 19
5% 15 15 15 17 19
10% 15 17 17 17 17

ing capacity of the attacked–concrete specimen (fT  A) is consid-

ered as a summation of the bearing capacity of the deteriorated
concrete (fc  Ac) and the healthy concrete (fss  As).
The relationship between the three strengths is described by Eq.
(6) according to a Taylor–type homogenization [57,58]:

f t  A ¼ f c  Ac þ f ss  As
Therefore, the average compressive strength of the deterio-
rated–area concrete can be calculated according to Eq. (7):
f ss ¼ ðf T  A  f c  Ac Þ=As
where fT, fc, and fss represent the compressive strengths of the
whole attacked–concrete specimen, healthy area, and deteriorated
area, respectively, and A, Ac, and As represents the total area,
healthy area, and deteriorated area of the attacked concrete, respec-
ð8Þ
Fig. 13. Integral area of sulfate ions distributions.
tively. In this study, the value of fc is assumed to be equal to the
ð9Þ compressive strength measured from the compressive testing on
the concrete specimens soaked in water.
In this study, the sulfate ions mainly concentrate in the outer
regions, and the sulfate attack depth is always within 20 mm.
For simplifications, the range from concrete surface to a depth of
11
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Table 5
The integral areas of sulfate ions distributions (mm%).

W/C Concentrations (%) 60 d 120 d 180 d 240 d 300 d

0.37 3% 0.424 1.115 1.5632 3.809 6.941
5% 1.477 3.405 3.6867 6.403 12.948
10% 2.197 5.316 8.4291 11.100 17.387
0.47 3% 3.006 8.000 10.918 11.993 17.960
5% 4.864 8.881 11.420 16.566 21.529
10% 9.344 12.628 16.728 18.498 26.074
0.57 3% 7.264 12.321 14.348 25.538 28.693
5% 14.266 16.171 17.486 22.066 28.908
10% 14.401 20.004 24.106 29.472 31.315

Fig. 14. Schematic diagram of sulfate-attacked concrete.

20 mm is considered as the deteriorations area. Thus, the integral
area of sulfate ions distributions within 5 mm to 20 mm is calcu-
lated to identify the deteriorations level of concrete specimens.
4.2. Degradations of mechanical properties
The degradations of the compressive strength of deteriorated–
area concrete is presented in Fig. 15. The compressive strength of
all groups of concrete specimens that underwent sulfate attack
presents a similar change. It initially increases with attack time
and decreases as further deteriorations occurs. The concrete spec-
imens with a higher W/B and in a higher concentrations of sulfate
solutions show a greater increase of compressive strength initially
followed by a greater decrease during the falling stage.
5. A novel strength assessment method based on sulfate ions
distributions
5.1. Basic assumptions and indicator
Sulfate ions from outside environment diffuse into concrete
based on the Fick’s law, combining with the C-S-H gel of the con-
12
crete matrix thus destroying the bonding strength among aggre-
gates and cement matrix [13,14]. Meanwhile, sulfate ions react
with the cement hydrations product to form soft and soluble gyp-
sum. subsequently, this gypsum reacts with the alumina to form
ettringite. Initially, ettringite crystals mainly deposit in the initial
air voids of concrete. With the further reactions, too excessive
amount of ettringite lead to expansive stress and cracks [15–17].
The newly generated cracks make the concrete more porous, sus-
ceptible to further sulfate attack, which leads to a high-rate reduc-
tion in strength [20]. The deterioration is not uniform across in
concrete, namely, the damage decreases along with depth. There-
fore, concrete under sulfate attack could be divided into two main
parts, including attacked part and healthy part shown in the
Fig. 16. Because sulfate attack only concentrates in attacked part
of concrete, so the strength of healthy part of concrete can be
assumed to be equal to the strength of normal concrete. Thus,
the key to strength assessment of deteriorated concrete is to esti-
mate the compressive strength of the damaged area of concrete.
Based on the analysis presented in the previous sections, the
integral area of sulfate ions distributions can be used as a better
indicator to express the process of sulfate attack and reveal the
influence of the W/B and concentrations of sulfate solutions on
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Fig. 15. Compressive strength of deteriorated area of concrete.

Fig. 18. Schematic diagram of assessment method of sulfate attacked concrete.

13
H. Cheng, T. Liu, D. Zou et al.
Fig. 16. The process of sulfate attack.
Fig. 17. The relationship between integral area and strength.
the attack process. Furthermore, compared to mass loss ratio and
dynamic elastic modulus, this indicator is in a continuous accumu-
lations process without an initial increasing stage or a falling stage,
which can more accurately identify the deteriorations level of con-
crete. Most importantly, in the actual applications conditions, com-
14
Construction and Building Materials 293 (2021) 123550
pared to currently assessing indicators, the distributions of sulfate
ions can be directly measured by sampling small portions of con-
crete. Therefore, the integral area of sulfate ions distributions is
considered as the primary indicator to assess the compressive
strength of attacked concrete.
In this experiment, the deteriorated area is considered as the
range from the surface of the concrete to the depth of 20 mm,
where sulfate ions are mainly concentrated. The formulations
between the integral area of sulfate ions distributions and com-
pressive strength is established to for strength assessment. Even
though the sulfate ions content of each layer is determined by
using the average sulfate content measured in the powder of four
concrete samples, the influence of randomly distributed aggregate
on sulfate ions distributions cannot be overlooked. Thus, in this
study, in order to mitigate this negative influence, random sample
consensus (RANSAC) was used to establish the relationship
between the integral area of sulfate ions content and compressive
strength of attacked part of concrete shown in the Fig. 17. The
RANSAC algorithm is a parameter estimations approach used to
fit a model to experimental data with many outliers. The algorithm
generates solutions using a minimum number of random data
points that are required to estimate the model parameters. The
model identifies how many points are classified as inliers (i.e.
points that fit the model) according to a predetermined tolerance.
The fractions of inliers over the total number of points in the set is
used to select the model with larger consensus through an iterative
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

Fig. 19. Strength comparison between M1, M2, and M3.

process where the data is resampled a fixed number of times sulfate ions distributions. The residual_threshold is maximum
[59,60]. In this study, RANSAC regressor algorithm from scikit- residual for a data sample to be classified as an inlier. By default,
learn was carried out to establish the relationship between com- the threshold is chosen as the MAD (median absolute deviations)
pressive strength of attacked area of concrete and integral area of of the target dataset (compressive strength of attacked area of con-

Fig. 20. verifications test.

15
H. Cheng, T. Liu, D. Zou et al.
Table.6
Comparison of various assessment methods.
Experiment
fs (MPa) 17.97
Error (%) 0 11.02
crete). In this study, the MAD is determined by automated multi-
round calculation, which is 7.73 MPa. The outlier refers to the inte-
gral area of sulfate ions distributions which is heavily influenced
by randomly distributed aggregates.
The equations for assessing the deteriorations of compressive
strength is:
f ss ¼ 1:0796  S þ 43:8714 ð10Þ
where fss represents the compressive strength of attacked-area con-
crete; S represents the integral area of sulfate ions distributions.
5.2. Assessment methodology
The deteriorated concrete is divided into two areas, including
the deteriorated area and healthy area. The strength of the healthy
area of concrete is assumed to equal to the strength of concrete
specimens in water. The strength of the damaged area of concrete
can be calculated using Eq. (10) by using measured integral area of
sulfate ions distributions. Based on the theory of homogenizations,
the strength of attacked concrete can be calculated using the com-
binations of healthy and damaged parts. The detailed procedures
are presented in Fig. 18.
5.3. Verifications of assessment methodology
To carry out verification analysis on the proposed method, con-
crete specimens with water-binder ratio 0.37, subjected to 3%, 5%
and 10% sulfate solution, are used to prove the accuracy and feasi-
bility of the new method (denoted as M3). Two additional predic-
tions methods are also used to assess the compressive strength of
concrete specimens. M1 represents the method proposed by Jiang
[61]. The compressive strength of sulfate-attacked concrete could
be predicted by the sulfate attack time, the concentrations of sul-
fate solutions, and the W/B. M2 refers to the method established
by Cao [62]. In his study, the time-dependent stress strain relation-
ship of sulfate-attacked concrete in a compressive state and dry–
wet cycles were proposed. The compressive strength of sulfate-
attacked concrete could be calculated by determining the attack
time, W/B, sulfate solutions concentrations, elastic modulus, peak
strain, and compressive state. Based on the strength comparison
between M1, M2, and M3 shown in the Fig. 19, M3 achieves the
smallest error in all 15 cases considered. Therefore, it can conclude
that the proposed method, M3 is not only reliable but also more
accurate for short- and long-term strength assessment of sulfate
attacked concrete.
A further verification was carried out by conduction a long-term
(360 days) strength prediction. Both mechanical tests and chemical
titrations experiments were conducted on the concrete specimens
with W/B of 0.47 after 360 days of sulfate attack exposed to 10%
Na2SO4 solutions. The strength of the healthy area of concrete is
assumed to equal to the strength of concrete in water after
300 days. According to the experimental results of concrete in
water, the hydrations process was almost complete after 300 days;
the compressive strength is 27.5 MPa. The compressive strength of
sulfate–attacked concrete after 360 days of exposure is 17.97 MPa,
as presented in Fig. 20(a). The sulfate ions distributions of sulfate–
attacked specimens is presented in Fig. 20(b). Given that the
16
Construction and Building Materials 293 (2021) 123550
M1 M2 M3
19.95 19.72 19.27
9.74 7.2
surface concrete was severely damaged, the sulfate ions became
concentrated in the third layer. From 5 mm to 19 mm, the sulfate
ions content decreased with depth. The integral area of sulfate ions
distributions is 30.57 (mm%).
Further comparison is presented in Table 6. Two additional pre-
dictions methods are used to predict the compressive strength of
concrete specimens. In this verifications process, the sulfate attack
time is 360 days, the W/B is 0.47, the concentration of the sulfate
solutions is 10%, and the compressive state is 0 MPa. M3 represents
the method proposed in the present study. As shown in Table 5, the
errors for each method are 11.02%, 9.74%, and 7.20%, respectively.
Notably, M3 can fit the measurements well and has a smaller rel-
ative error. It can thus be concluded that the proposed method
based on the sulfate ions distributions and homogenizations the-
ory can be used as a more accurate method to predict the compres-
sive strength of concrete under sulfate attack in a long term.
Most importantly, compared to other strength assessment
methods, the only requirement for this proposed method is to
measure sulfate ions distribution, which makes this method easier
and more practicable than other assessment methods. Because, in
actual conditions, it is difficult to determine accurate attack time,
elastic modulus and peak strain. Therefore, the newly proposed
assessment method based on sulfate ions distributions and
homogenizations provides a potential application in assessing the
loading capacity of actual concrete structures exposed to aggres-
sive environments.
6. Conclusions
This study investigated the deteriorations progress of concrete
exposed to sulfate attack and dry–wet cycle. The non–uniform
damage characteristics of sulfate–attacked concrete were dis-
cussed by dividing the concrete specimens into deteriorated area,
and healthy area. A new indicator, the integral area of sulfate ions
distributions, was proposed to express the deteriorations progress
of attacked concrete, and a novel assessment method based on sul-
fate ions distributions was established. The conclusions are sum-
marized as follows:
(1) The mass loss ratio and dynamic elastic modulus of sulfate–
attacked concrete present three main stages: a rapidly
increasing stage, a steadily increasing stage, and a dropping
stage. Additionally, the compressive strength presents two
main stages: an initially increasing stage and a continuously
dropping stage. Notably, a higher solutions concentration
does not always lead to a greater increase in mass or
dynamic modulus at the early increasing stage.
(2) Compared to the sulfate attack depth, the integral area of
sulfate ions distributions is a better indicator to describe
the progress of sulfate attack. The index of the integral area
increases monotonously with deteriorations time.
(3) The established formulation between compressive strength
and integral area of sulphate ions distributions can be used
to determine the deterioration of sulfate–attacked concrete.
The proposed assessment method can be used to accurately
and practically assess the loading capacity of actual concrete
structures exposed to aggressive environments.
H. Cheng, T. Liu, D. Zou et al. Construction and Building Materials 293 (2021) 123550

[24] B. Tian, M.D. Cohen, Does gypsum formations during sulfate attack on concrete
lead to expansions?, Cem. Concr. Res. 30 (2000) 117–123.
Declaration of Competing Interest [25] American Society for Testing and Materials, Standard Test Method for Length
Change of Hydraulic-Cement Mortars Exposed to a Sulfate Solutions, ASTM
The authors declare that they have no known competing finan- C1012. West Conshohocken, United States, 2015.
[26] Chinese Nationsal Standard, Standard for Test Method of Long-term
cial interests or personal relationships that could have appeared Performance and Durability of Ordinary concrete, GB 50082-2012. Beijing,
to influence the work reported in this paper. China, 2012.
[27] Z. Zhang, J. Zhou, J. Yang, Y. Zou, Z. Wang, Understanding of the deterioration
characteristic of concrete exposed to external sulfate attack: insight into
Acknowledgments mesoscopic pore structures, Constr. Build. Mater. 260 (2020) 119932.
[28] Z.Y. Zhang, J.T. Zhou, J. Yang, Y. Zou, Z.S. Wang, Cracking characteristics and
This study was financially supported by the National key pore development in concrete due to physical attack, Mater. Struct. 53 (2020)
1–13.
research and development program of China (Grant No. [29] D.J. Zou, H.B. Cheng, T.J. Liu, S.S. Qin, T.H. Yi, Monitoring of concrete structure
2019YFC1511005), National Science Fund for Distinguished Young damage caused by sulfate attack with the use of embedded piezoelectric
Scholars (Grant No. 52025081), National Natural Science Founda- transducers, Smart Mater. Struct. 28 (2019) 1275–1296.
[30] L. Guo, Y. Wu, P. Duan, Z. Zhang, Improving sulfate attack resistance of
tions of China (Grant No. 51978211), Key Research and Develop- concrete by using calcined Mg-Al-CO3 LDHs: Adsorptions behavior and
ment Program of Guangdong Province (Grant No. mechanism, Constr. Build. Mater. 232 (2020) 117256.
2019B111107001), and Shenzhen Science and Technology Program [31] D. Mostofinejad, S.M. Hosseini, F. Nosouhian, T. Ozbakkaloglu, B.N. Tehrania,
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(Grant No. RCYX20200714114525013). and milled waste glass in magnesium sulfate environment, J. Build. Eng. 29
(2020) 101182.
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