materials

Article
Degradation Mechanism of Concrete Subjected to
External Sulfate Attack: Comparison of Different
Curing Conditions
Gaowen Zhao 1,2, *, Mei Shi 3, *, Mengzhen Guo 1 and Henghui Fan 4
1 School of Highway, Chang’an University, Xi’an 710064, China; yubi_shangguan@163.com
2 Department of Geotechnical Engineering, Tongji University, Shanghai 200092, China
3 College of Natural Resources and Environment, Northwest A&F University, Yangling 712100, China
4 College of Water Conservancy and Architectural Engineering, Northwest A&F University, Yangling 712100,
China; yt07@nwsuaf.edu.cn
* Correspondence: 007gwzhao@chd.edu.cn (G.Z.); meishi@nwafu.edu.cn (M.S.)




Received: 4 June 2020; Accepted: 14 July 2020; Published: 16 July 2020


Abstract: Sulfate induced degradation of concrete brings great damage to concrete structures in saline
or offshore areas. The degradation mechanism of cast-in-situ concrete still remains unclear. This paper
investigates the degradation process and corresponding mechanism of cast-in-situ concrete when
immersed in sulfate-rich corrosive environments. Concrete samples with different curing conditions
were prepared and immersed in sulfate solutions for 12 months to simulate the corrosion of precast
and cast-in-situ concrete structures, respectively. Tests regarding the changes of physical, chemical,
and mechanical properties of concrete samples were conducted and recorded continuously during the
immersion. Micro-structural and mineral methods were performed to analyze the changes of concrete
samples after immersion. Results indicate that the corrosion process of cast-in-situ concrete is much
faster than the degradation of precast concrete. Chemical attack is the main cause of degradation for
both precast and cast-in-situ concrete. Concrete in the environment with higher sulfate concentration
suffers more severe degradation. The water/cement ratio has a significant influence on the durability
of concrete. A lower water/cement ratio results in obviously better resistance against sulfate attack
for both precast and cast-in-situ concrete.

Keywords: cast-in-situ concrete; degradation mechanism; sulfate attack; sulfate diffusion

1. Introduction
Sulfates, chlorides, and other corrosive sources are widely observed in soils, ground water, river
water, and seawater in salty saline and offshore areas [1–5]. Among the mostly observed ions in the
environment, sulfates have been claimed to be one of the most aggressive ions to bring great damage
to concrete structures [6–11].
Experimental and theoretical studies regarding the degradation of concrete caused by sulfate
attack have been well reported in recent decades. The corrosion products such as ettringite, gypsum, or
thaumasite were reported after sulfate corrosion [12,13]. In addition, researchers found that hydrates of
sulfates, especially mirabilite, were responsible for the development of cracks in concrete in sulfate-rich
environments [14,15]. Meanwhile, some researchers proposed that both chemical and physical attack
induced by sulfate presence should be considered, which directly lead to the degradation of concrete,
since both chemical corrosion products and crystallization hydrates have been detected in the damaged
concrete [16]. Therefore, it is widely accepted that the degradation of concrete induced by sulfate attack
can be divided into physical sulfate attack, chemical sulfate attack, and physical–chemical combined
degradation [17,18].

Materials 2020, 13, 3179; doi:10.3390/ma13143179 www.mdpi.com/journal/materials

Materials 2020, 13, 3179 2 of 17

Concrete subjected to sulfate attack always results in great expansion as well as the risk of
failure [19–21]. The expansion is reported to be caused by the corrosion products or hydrates induced
during sulfate attack [22,23]. It has been reported that the volume of chemical corrosion products,
especially ettringite, far surpasses the volume of reactants during chemical corrosion [24–26]. In addition,
the strength of corrosion products is relatively low, leading to a great decrease of concrete strength [27].
It is notable that the volume of hydrates, Na2 SO4 ·10H2 O, is several times greater than the volume of
Na2 SO4 [28–30]. Therefore, chemical or physical attack by sulfates has a significant negative effect on
the performance of concrete [31].
It is clear that previous studies regarding the degradation of concrete induced by sulfate attack are
of great importance for further research. By paying close attention to the published research, most of the
previous studies were conducted on precast concrete samples. However, it should be pointed out that
most concrete structures in salty saline or offshore areas are cast-in-situ concrete structures, especially
for underground concrete structures. It should be noted that the construction processes of precast
and cast-in-situ concrete structures are quite different. For cast-in-situ concrete, the corrosion process
starts immediately after the casting of fresh concrete in the sulfate-rich environments, while for precast
concrete structures, the hardening process has finished before being installed in the environment.
Moreover, the effects of the water/cement ratio on the sulfate induced degradation of cast-in-situ
concrete are rarely reported, which plays an important role in affecting the properties and safety of
cast-in-situ structures. Consequently, the degradation process and mechanism between the precast and
cast-in-situ concrete are quite different. Moreover, the safety of cast-in-situ concrete cannot be ensured
if the design of cast-in-situ concrete structures is based on the research conducted on precast concrete
samples. Thus, it is necessary to perform a specific experiment to reveal the degradation process and
mechanism differences between the precast and cast-in-situ concrete.
To study the degradation process and mechanism of cast-in-situ concrete caused by sulfate attack,
concrete samples in cylinder shapes were prepared and immersed in sulfate solutions. Different curing
conditions were used in the present study. To highlight the differences of specimens with different curing
conditions, specimens cured for 12 h were described as cast-in-situ concrete and specimens cured for 28
days were described as precast concrete in the present study. Tests were conducted to record the physical,
chemical, and mechanical properties changes during the 12-month immersion. The micro-structural
and mineral properties of concrete were analyzed after immersion by X-ray diffraction (XRD), energy
dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM) tests.

2. Materials and Methods

2.1. Materials
To prepare concrete specimens, P.C. 32.5 R Portland cement (Conch, Shanghai, China) was used in
the present experiment [32,33]. The chemical composition of cement is presented in Table 1. River sand
was used in this study as fine aggregate. The maximum particle size was 2.36 mm, and the fineness
modulus was 2.6. Artificial crushed stone was used as coarse aggregate. Excessively large aggregate in
concrete would result in great discreteness of the test results due to the size of specimens, thus the
maximum size of crushed stone was 10 mm. Distilled water was used to prepare concrete samples and
sulfate corrosive solutions.

Table 1. Chemical components of cement.

Chemical Components Al2 O3 SO3 Fe2 O3 MgO CaO

Content (%) 6.82 1.96 2.13 1.92 60.05

To investigate the effects of water/cement ratio on the degradation of concrete caused by sulfate
attack, three kinds of concrete samples were designed in the present study. Mixture proportions of
concrete samples in the present study are listed in Table 2.
Materials 2020, 13, 3179 3 of 17

Table 2. Mixture proportions of concrete in the present study.

Concrete Components
w/c
Water (kg/m3 ) Cement (kg/m3 ) Sand (kg/m3 ) Gravel (kg/m3 )
0.40 162 405 600 1275
0.48 175 365 638 1238
0.55 189 345 685 1210
Note: w/c is the water/cement ratio.

2.2. Sample Preparation and Testing Methods

2.2.1. Sample and Solution Preparation

Na2 SO4 was selected to prepare sulfate corrosive solutions. The sulfate concentrations of different
solutions were set at 0%, 3%, 5%, and 10% (named as CK, 3S, 5S, and 10S, as shown in Table 3) in
the present study. It should be noted that the sulfate concentration and liquid depth of each solution
were checked every month to ensure that the sulfate concentration was constant and all the specimens
were fully immersed in the solutions. The details of specimens and solutions are presented in Table 3.
It should be emphasized that to get a relatively accurate value of concrete properties, three parallel
tested samples were prepared simultaneously in different tests in the present study.

Table 3. The details of specimens and solutions.

Specimens Immersion Solution Specimens Immersion Solution

PCK Distilled water CCK Distilled water
P3S 3% Na2 SO4 solution C3S 3% Na2 SO4 solution
P5S 5% Na2 SO4 solution C5S 5% Na2 SO4 solution
P10S 10% Na2 SO4 solution C10S 10% Na2 SO4 solution
Note: P for precast concrete specimens and C for cast-in-situ concrete specimens.

Raw materials, such as river sand, crushed stone, and cement, were weighed and mixed in the
mixer before the distilled water was added. Freshly mixed concrete was then put in the modules, and
the size of concrete specimens was 100 mm × 200 mm (diameter × height). Samples with modules were
then put in the curing chamber with a temperature of 22 ◦ C and relative humidity of >95%. The top
and bottom surfaces of each specimen were sealed with epoxy resin. For precast concrete, the samples
were cured for 28 days before being put into the solutions, while for cast-in-situ concrete, the samples
were put into the solutions after being cured for 12 h.

2.2.2. Physical Properties

It should be noted that the specimens were put into an oven at a temperature of 60 ◦ C for 48 h
after being immersed in the solutions for 1, 3, 6, 9, and 12 months. To determine the diameter and
weight changes of concrete samples during the immersion, a Vernier caliper and an electronic scale
were selected to measure the diameter and weight of specimens. The diameter of each specimen was
measured 5 times near the mid-height of specimens to obtain an average diameter. The weight of each
specimen was weighed twice, and the average value was recorded.

2.2.3. Compressive Strength

An unconfined compressive strength test was performed to determine the compressive strength
of each specimen during the immersion. A loading system (the equipment model was POPWIL (HSR))
with a maximum capacity of 1000 kN was used to conduct the compressive strength test, and the
loading rate during the tests was set as 5 kN/s.
the loading rate during the tests was set as 5 kN/s.

2.2.4. Sulfate Concentration

To determine
Materials the
2020, 13, 3179 sulfate concentration in the concrete specimens, a drill was used to collect 4 of 17the
powder samples by drilling perpendicular to the lateral surface of each specimen. Five powder
samples (from the surface to a depth of 25 mm beneath the exposed surface of specimens) were
2.2.4. Sulfate
obtained Concentration
and sealed in the plastic zip bags. Each powder sample was mixed with 50 mL distilled
water and put into athe
To determine bottle forconcentration
sulfate 48 h. Then the solution
in the was
concrete filtered through
specimens, filter
a drill was paper
used to remove
to collect the
residues.
powder The sulfate
samples concentration
by drilling of each
perpendicular solution
to the was then
lateral surface determined
of each specimen. by
Fivestandard chemical
powder samples
titration [34].
(from the surface to a depth of 25 mm beneath the exposed surface of specimens) were obtained and
sealed in the plastic zip bags. Each powder sample was mixed with 50 mL distilled water and put into
2.2.5. Micro-Structural
a bottle for 48 h. Thenand
the Mineral
solution Analyses
was filtered through filter paper to remove residues. The sulfate
concentration of each solution was then determined by standard chemical titration [34].
SEM (by ZEISS-SIGMA 300 system, Carl Zeiss (Shanghai), Shanghai, China) and XRD (by model
RINT 2000
2.2.5. X-ray diffractometer,
Micro-Structural Rigku
and Mineral (Beijing), Beijing, China) analyses were performed to observe
Analyses
the micro-structures and to determine the mineral composition of concrete samples after being
SEM (by ZEISS-SIGMA 300 system, Carl Zeiss (Shanghai), Shanghai, China) and XRD (by model
immersed in sulfate solutions for 12 months. The element analysis (by EDS (ZEISS-SIGMA 300, Carl
RINT 2000 X-ray diffractometer, Rigku (Beijing), Beijing, China) analyses were performed to observe the
Zeiss (Shanghai), Shanghai, China)) was also performed in the SEM test to determine the corrosion
micro-structures and to determine the mineral composition of concrete samples after being immersed
products. The samples used in the SEM analysis were concrete core samples drilled from the lateral
in sulfate solutions for 12 months. The element analysis (by EDS (ZEISS-SIGMA 300, Carl Zeiss
surface of specimens
(Shanghai), Shanghai,with a depth
China)) was of 10performed
also mm beneath theSEM
in the exposed
test tosurface. Thethe
determine powder samples
corrosion used
products.
in The
the XRD analysis were drilled from the exposed surface with a depth of 5 mm and passed
samples used in the SEM analysis were concrete core samples drilled from the lateral surface ofthrough
a 75-µm sieve.
specimens with a depth of 10 mm beneath the exposed surface. The powder samples used in the XRD
analysis were drilled from the exposed surface with a depth of 5 mm and passed through a 75-µm sieve.
3. Results and Discussion
3. Results and Discussion
It is well accepted that the micro-structural and mineral properties play an important role in
affectingIt is
thewell accepted
basic that
physical andthe micro-structural
mechanical and of
properties mineral properties
concrete playTherefore,
structures. an important role in of
the results
affecting the basic physical and mechanical properties of concrete structures. Therefore,
the micro-structural and mineral analyses were given and discussed firstly. Additionally, sulfates the results
of the micro-structural
penetrate and mineral
concrete and react analysescompositions
with concrete were given and discussedcorrosion
to generate firstly. Additionally,
products andsulfates
hence
penetrate concrete and react with concrete compositions to generate corrosion products and
change the properties of concrete. Thus, the diffusion process of sulfates into concrete is subsequently hence
change theFinally,
introduced. properties of concrete.
results of otherThus, the diffusion
properties process
are given and of sulfates into concrete is subsequently
discussed.
introduced. Finally, results of other properties are given and discussed.
3.1. Micro-Structural and Mineral Analyses
3.1. Micro-Structural and Mineral Analyses
ToToshow
showthe
the micro-structures
micro-structures ofofconcrete
concrete after
after immersion
immersion in sulfate
in sulfate solutions
solutions for 12 for 12 months,
months, SEM
SEM observation was conducted, and the results are presented in Figure 1. SEM images
observation was conducted, and the results are presented in Figure 1. SEM images in Figure 1a,b were in Figure
1a,b were taken from precast concrete and cast-in-situ concrete specimens after immersion
taken from precast concrete and cast-in-situ concrete specimens after immersion in 10% sulfate solution in 10%
sulfate
for 12solution
months,for
with12the
months, with the same
same water/cement water/cement
ratio ratioa relatively
of 0.55. To give of 0.55. To givedetermination
solid a relatively solid
of
determination of the corrosion products after immersion. XRD tests were performed
the corrosion products after immersion. XRD tests were performed on different concrete samples on different
concrete samples after
after immersion, andimmersion, andshown
the results are the results are shown
in Figure 2. TheinEDSFigure 2. The
analysis EDS analysis
results results
are also listed onare
also
the right side of the SEM images to give reliable proof. The results of XRD analysis in Figure 2a,b in
listed on the right side of the SEM images to give reliable proof. The results of XRD analysis
Figure
were 2a,b werefrom
obtained obtained fromand
the precast thecast-in-situ
precast and cast-in-situ
concrete concrete
specimens specimens
immersed in 10%immersed in 10%
sulfate solution,
and the
sulfate water/cement
solution, and theratios were 0.55.ratios were 0.55.
water/cement

(a)
Figure 1. Cont.
Materials 2020,
Materials 13, 13,
2020, 3179x FOR PEER REVIEW 5 of5 17
of 17
Materials 2020, 13, x FOR PEER REVIEW 5 of 17

(b)
(b)
Figure 1. SEM images and corresponding EDS results in concrete exposed to 10% sulfate solutions for
Figure SEM images
1. SEM images and corresponding
corresponding EDS results
results in concrete
concrete exposed to 10% sulfate solutions for
(a) precast concrete,and
magnification = 5 K, and (b) cast-in-situ concrete, magnification = 2.5 K.
magnification =
(a) precast concrete, magnification = 5 K, and (b) cast-in-situ concrete, magnification =
= 2.5 K.
□
□□ ◆E □ SiO2
□ ◆ E◇ G □ ★
SiO 2
Sodium Sulfate Hydrate
◇ G ★Sodium Sulfate Hydrate

□
□
□
□ □
□
□ □ □
◇ □
◆ ◆◇ □ □ □
◇
◆ ◆ ★◆
◆ ◇ ◇ □
◆ ◇ ◆ ◇
◆ ◇ ★ ◆ ★
◆
◇ ◇ ◆ ◇
◆ ◆ ◇ ◇ ★ ◇
◇ ★ ★ ◇

10 20 30 40 50 60 70
10 20 30 40 50 60 70
2θ
2θ(a)
(a)
□
□
□ ◆E □ SiO2
□ ◆ E◇ G □ ★
SiO
Sodium
2 Sulfate Hydrate
◇G ★Sodium Sulfate Hydrate

□
□

□
□ □
□ □ □
□ □
◇◆ □ □
◆ ★ ◆ ◇ □
◇ ★ ◇◆◆ ◆ ◇□
◇◇ ◇
◆
◇ ★
◆
◆
★ ◆
◇◆ ◇ ◆ ◇
◆ ◆ ◇ ★
◇
★

10 20 30 40 50 60 70
10 20 30 40 50 60 70
2θ
2θ(b)
(b)
Figure
Figure2. 2.XRD
XRDanalysis
analysisresults
resultsof
of corrosion
corrosion products in
in the
theconcrete
concretefor
for(a)
(a)cast-in-situ
cast-in-situconcrete,
concrete,
and
Figure
and 2. XRDconcrete.
(b)precast
(b) precast analysis
concrete.results of corrosion products in the concrete for (a) cast-in-situ concrete, and
(b) precast concrete.
It is clear in the SEM images and EDS analysis results that sulfate corrosion products such as
It is clear
ettringite andingypsum
the SEMwere
images and EDS
observed analysis
in both results
precast and that sulfate concrete
cast-in-situ corrosionsamples.
products
It such as be
should
ettringite and gypsum were observed in both precast and cast-in-situ concrete samples. It should be
Materials 2020, 13, 3179 6 of 17

It is clear in the SEM images and EDS analysis results that sulfate corrosion products such as
ettringite and gypsum were observed in both precast and cast-in-situ concrete samples. It should be
noted that the peaks of Au and S shared little overlap in the EDS results, and a and b in the SEM
images in Figure 1 were the sampling points of EDS analysis. The analysis results of XRD tests also
indicated that the peaks of corrosion products of ettringite (marked as E in XRD patterns), gypsum
(marked as G in XRD patterns), and sulfate hydrates were detected in the concrete after immersion in
sulfate solutions. The involved chemical corrosion reactions of sulfate attack can be summarized as
follows [35–37]:
2Na+ + SO4 2− + 10H2 O ⇔ Na2 SO4 · 10H2 O (1)

3CaO · Al2 O3 + 3(CaSO4 · 2H2 O) + 26H2 O → 3CaO · Al2 O3 · 3CaSO4 · 32H2 O (2)

3CaO · Al2 O3 · CaSO4 · 12H2 O + 2(CaSO4 · 2H2 O) + 16H2 O → 3CaO · Al2 O3 · 3CaSO4 · 32H2 O (3)

4CaO · Al2 O3 · 13H2 O + 3(CaSO4 · 2H2 O) + 14H2 O → 3CaO · Al2 O3 · 3CaSO4 · 32H2 O + CaO · H2 O (4)

Ca(OH)2 +Na2 SO4 +2H2 O → CaSO4 · 2H2 O + 2NaOH (5)

The results of micro-structural and mineral analyses illustrate that the main corrosion products
in both precast and cast-in-situ concrete were the same. Thus, one can conclude that both precast
and cast-in-situ concrete mainly suffer chemical sulfate attack, especially when the concrete is fully
immersed in the sulfate-rich environments. The peaks of sulfate hydrates detected in concrete indicated
that crystallization of sulfates also occurred in the cracks and pores of concrete. However, it should
be emphasized that fully immersed concrete samples stayed beneath the liquid surface all the time,
and the evaporation process was not involved during the immersion. Thus, it was inferred that the
crystallization hydrates of sulfates were generated during the 48-hours drying process instead of the
immersion period.
The generation of sulfate corrosion products would generally affect the properties of concrete
in the following three ways. Firstly, the corrosion products would be generated and embedded in
concrete, affecting the subsequent development of other properties. The reason is that the properties
of sulfate-induced corrosion products and concrete are quite not the same. Secondly, the generated
corrosion products would be gradually accumulated in the initial cracks and pores in concrete,
influencing the density and strength of the outer layer of concrete. At last, it is well accepted that the
corrosion products would cause great volume expansion by loading great pressure on the walls of
internal cracks and pores, putting the outer layer of concrete under great tensile stress.

3.2. Sulfate Concentration

Concentration of sulfates in different concrete samples was determined, and the results are shown
in Figure 3. Overall, the results clearly indicated that the concentration of sulfates was relatively high
near the surface, and then decreased fast with the growth of depth beneath the exposed surface of
concrete specimens.
For precast concrete specimens, it is clear that the penetration of sulfate ions was relatively slow,
especially for concrete immersed in 3% sulfate solution. The concentration of sulfates in concrete
immersed in 5% and 10% sulfate solutions was higher and the penetration depth was deeper. Moreover,
it is clear that the sulfate concentration in concrete with lower water/cement ratio is lower than that in
concrete with greater water/cement ratio.
As for cast-in-situ concrete, it was noticed that the sulfate concentration was relatively higher
than that in precast concrete specimens. In addition, sulfates reached deeper depth in cast-in-situ
concrete. Thus, sulfates diffused faster in cast-in-situ concrete, especially for concrete specimens with
high water/cement ratio.
 Materials 2020, 13, 3179 7 of 17
Materials 2020, 13, x FOR PEER REVIEW 7 of 17

6
C10S(1 Months)
C10S(3 Months)
5 C10S(6 Months)
C10S(9 Months)

Sulfate Concentration (%)

4 C10S(12 Months)
P10S(1 Months)
P10S(3 Months)
3
P10S(6 Months)
P10S(9 Months)
2 P10S(12 Months)

0
0 4 8 12 16 20 24
Depth (mm)
(a)
4
CCK(12 Months)
C3S(12 Months)
C5S(12 Months)
3 C10S(12 Months)
Sulfate Concentration (%)

PCK(12 Months)
P3S(12 Months)
P5S(12 Months)
2 P10S(12 Months)

0
0 4 8 12 16 20 24
Depth (mm)
(b)
4
CCK(12 Months)
C3S(12 Months)
C5S(12 Months)
3 C10S(12 Months)
Sulfate Concentration (%)

PCK(12 Months)
P3S(12 Months)
P5S(12 Months)
2 P10S(12 Months)

0
0 4 8 12 16 20 24
Depth (mm)
(c)
Figure 3. Cont.
 Materials 2020, 13, 3179 8 of 17
Materials 2020, 13, x FOR PEER REVIEW 8 of 17

CCK(12 Months)
4 C3S(12 Months)
C5S(12 Months)
C10S(12 Months)

Sulfate Concentration (%)

3 PCK(12 Months)
P3S(12 Months)
P5S(12 Months)
P10S(12 Months)
2

0
0 4 8 12 16 20 24
Depth (mm)
(d)
Figure
Figure 3. 3. Sulfate
Sulfate concentrationofofconcrete
concentration concretewith
with different
different water/cement
water/cementratios:
ratios:(a)
(a)0.55,
0.55,inin10%
10%sulfate
sulfate
solution, (b) 0.40, in different solutions, (c) 0.48, in different solutions, and (d) 0.55, in different
solution, (b) 0.40, in different solutions, (c) 0.48, in different solutions, and (d) 0.55, in different solutions.
solutions.
The diffusion of sulfates into concrete can be divided into two steps. In the first step, the soluble
sulfates such as Na2 SO4 dissolve in water to form a sulfate solution in which sulfate ions can move
For precast concrete specimens, it is clear that the penetration of sulfate ions was relatively slow,
freely. In the second step, sulfate ions would move from positions with higher sulfate concentrations
especially for concrete immersed in 3% sulfate solution. The concentration of sulfates in concrete
to positions with lower sulfate concentrations. In this regard, the diffusion of sulfate ions is mainly
immersed in 5% and 10% sulfate solutions was higher and the penetration depth was deeper.
motived by the concentration gradient between the concrete and the outer environments. In addition,
Moreover,
it shoulditbe is emphasized
clear that thethat sulfate concentration
the porosity in concrete
of concrete withan
also plays lower water/cement
important ratio is lower
role in affecting the
than that in concrete with greater water/cement ratio.
diffusion of sulfates. It is obvious that concrete with higher porosity can physically provide more paths
forAsthefor cast-in-situ
penetration concrete,Thus,
of sulfates. it wasthenoticed that the sulfate
sulfate concentration concentration
in concrete was relatively
with a higher water/cementhigher
than that in precast concrete specimens. In addition, sulfates reached deeper depth
ratio is relatively high, while on the contrary, sulfates only reach a shallower depth beneath the exposed in cast-in-situ
concrete.
surface Thus, sulfates
of concrete withdiffused
a lowerfaster in cast-in-situ
water/cement ratio. concrete, especially for concrete specimens with
high water/cement ratio.
It should be noted that the diffusion of sulfates in precast concrete and cast-in-situ concrete is
The diffusion
different. of sulfates
First of all, intocan
sulfate ions concrete
diffusecan be divided
directly into two
into concrete oncesteps. In the
the fresh first step,
concrete is putthe soluble
into the
sulfates such as Na SO dissolve in water to form a sulfate solution in which
environment during the hardening process. Then, the penetrated sulfate ions can react with the cement
2 4 sulfate ions can move
freely. In the second
composition step, sulfate
to generate sulfate ions wouldproducts
corrosion move from suchpositions
as gypsum with
andhigher sulfate
ettringite. Theconcentrations
embedded
to positions with lower sulfate concentrations. In this regard, the diffusion of sulfate ionsconcrete.
corrosion products affect the integrity of concrete and hence increase the initial porosity of is mainly
Additionally,
motived the strength of gradient
by the concentration sulfate induced
between corrosion products
the concrete andisthe
relatively low, making itIn
outer environments. easier for
addition,
it should be emphasized that the porosity of concrete also plays an important role in affectinginthe
expansive products to generate more cracks in the upcoming stage. Thus, the diffusion of sulfates
cast-in-situ
diffusion concrete It
of sulfates. is is
easier and faster
obvious than that with
that concrete in precast concrete
higher structures.
porosity can physically provide more
paths for the penetration of sulfates. Thus, the sulfate concentration inisconcrete
It is clear that the porosity of concrete with different water/cement ratios different. with
The porosity
a higher
is lower when the water/cement ratio is lower, resulting in better waterproofness.
water/cement ratio is relatively high, while on the contrary, sulfates only reach a shallower Thus, it woulddepth
be
harder for an external sulfate solution to permeate into the internal concrete areas and hence decreases
beneath the exposed surface of concrete with a lower water/cement ratio.
the diffusion speed of sulfate ions. Therefore, the sulfate concentration is low and the penetration
It should be noted that the diffusion of sulfates in precast concrete and cast-in-situ concrete is
depth is shallow in concrete with a lower water/cement ratio. Furthermore, concrete with a lower
different. First of all, sulfate ions can diffuse directly into concrete once the fresh concrete is put into
water/cement ratio has a higher tensile strength, making it difficult for sulfate corrosion products to
the environment during the hardening process. Then, the penetrated sulfate ions can react with the
generate new cracks, while for concrete with a high water/cement ratio, it would be easier for expansive
cement composition to generate sulfate corrosion products such as gypsum and ettringite. The
products to extend initial cracks or generate new cracks, leading to a faster degradation.
embedded corrosion products affect the integrity of concrete and hence increase the initial porosity
of concrete. Additionally, the strength of sulfate induced corrosion products is relatively low, making
it easier for expansive products to generate more cracks in the upcoming stage. Thus, the diffusion
of sulfates in cast-in-situ concrete is easier and faster than that in precast concrete structures.
It is clear that the porosity of concrete with different water/cement ratios is different. The
porosity is lower when the water/cement ratio is lower, resulting in better waterproofness. Thus, it
would be harder for an external sulfate solution to permeate into the internal concrete areas and
hence decreases the diffusion speed of sulfate ions. Therefore, the sulfate concentration is low and
the penetration depth is shallow in concrete with a lower water/cement ratio. Furthermore, concrete
with a lower water/cement ratio has a higher tensile strength, making it difficult for sulfate corrosion
Materials 2020, 13, x FOR PEER REVIEW 9 of 17

products to generate new cracks, while for concrete with a high water/cement ratio, it would be easier
for expansive products to extend initial cracks or generate new cracks, leading to a faster degradation.
Materials 2020, 13, 3179 9 of 17
3.3. Physical Properties
The diameter and weight of different specimens in different solutions were measured and
3.3. Physical Properties
recorded during the immersion. To give a clear comparison of diameter for different concrete
specimens, the change
The diameter andratios
weightofofdiameter were calculated
different specimens by solutions were measured and recorded
in different
during the immersion. To give a clear comparison of diameter for different concrete specimens, the
change ratios of diameter were calculated by d − d
a= t 0
×100% (6)
dt d
−0d0
a= × 100% (6)
d0
in which a is the change ratio, d0 is the initial diameter, and dt is the diameter of the specimen after a
in which a is the change ratio, d0 is the initial diameter, and dt is the diameter of the specimen after a
specific immersion period of t. The results are shown in Figure 4.
specific immersion period of t. The results are shown in Figure 4.

CCK PCK
0.003 C3S P3S
C5S P5S
C10S P10S
Diameter change ratio

0.002

0.001

0.000

0 2 4 6 8 10 12
Time (Month)
(a)
0.006
CCK PCK
C3S P3S
0.004 C5S P5S
C10S P10S
Diameter change ratio

0.002

0.000

-0.002
0 2 4 6 8 10 12
Time (Month)
(b)
Figure 4. Cont.
 Materials 2020, 13, 3179 10 of 17
Materials 2020, 13, x FOR PEER REVIEW 10 of 17

0.006
CCK PCK
C3S P3S
C5S P5S
0.004 C10S P10S

Diameter change ratio

0.002

0.000

-0.002
0 2 4 6 8 10 12
Time (Month)
(c)
Figure
Figure 4. 4. Diameter
Diameter change
change ratios
ratios forfor concrete
concrete with
with different
different water/cementratios:
water/cement ratios:(a)(a) 0.40,
0.40, (b)(b) 0.48,
0.48, and
and (c)
(c) 0.55. 0.55.

The comparison clearly indicates that concrete in sulfate solutions suffered radical expansion.
The comparison clearly indicates that concrete in sulfate solutions suffered radical expansion.
For precast concrete specimens, the diameter showed a relatively stable increase tendency during the
For precast concrete specimens, the diameter showed a relatively stable increase tendency during the
immersion. Only the specimen immersed in 10% sulfate solution showed a relatively slight decrease
immersion. Only the specimen immersed in 10% sulfate solution showed a relatively slight decrease
after the ninth month (with a water/cement ratio of 0.55). Additionally, one could observe that concrete
after the ninth month (with a water/cement ratio of 0.55). Additionally, one could observe that
in solution with a higher concentration of sulfates suffered more radical expansion in the early stage,
concrete in solution with a higher concentration of sulfates suffered more radical expansion in the
indicating that concrete suffered more serious degradation when immersed in the environments with a
early stage,higher
relatively indicating
sulfatethat concrete suffered more serious degradation when immersed in the
concentration.
environments with a relatively
Compared to precast concrete higherspecimens,
sulfate concentration.
it can be seen in Figure 4 that cast-in-situ concrete
Compared to precast concrete specimens,
obviously encountered more volume changes during it canthebe seen in Figure
immersion. As for 4concrete
that cast-in-situ
immersionconcrete
in 5%
obviously
and 10% encountered more volume
solutions, the radius increasedchanges during
quickly in the corrosion
the early immersion.stageAsbut
forsoon
concrete
beganimmersion
to decrease in
5%even
andafter
10%thesolutions, the radius
sixth month. increased
Moreover, quickly
one could in the
observe earlycracks
visible corrosion
on thestage butofsoon
surface began to
cast-in-situ
decrease
concreteeven after the
specimens. Thesixth month.
spalling Moreover,
and shedding of one could
concrete observe
powder andvisible cracks
fragments onalso
were theobserved
surface of
cast-in-situ concrete
on the surface specimens.
of concrete Thesulfate
in a 10% spalling and shedding of concrete powder and fragments were
solution.
also observed on the
For precast surfacesamples,
concrete of concrete
the in a 10%increased
weight sulfate solution.
quickly in the early corrosion stage and
For precast
became relativelyconcrete samples,
stable after the weight
nine months. increased there
Furthermore, quickly
wasina slight
the early corrosion
difference stagethe
between and
concrete in distilled water and sulfate solutions, which was caused by the accumulation
became relatively stable after nine months. Furthermore, there was a slight difference between the of sulfate
corrosion
concrete products.water
in distilled In addition, it can
and sulfate be seen that
solutions, whichconcrete immersed
was caused by thein accumulation
solutions with ofhigher
sulfate
sulfate concentration obviously experienced more fluctuation during the immersion,
corrosion products. In addition, it can be seen that concrete immersed in solutions with higher sulfate and the weight
increment wasobviously
concentration relatively greater, especially
experienced at the
more early stage.during
fluctuation However,theit can be seen that
immersion, the the
and weight of
weight
cast-in-situ concrete experienced more significant changes during the 12-month immersion.
increment was relatively greater, especially at the early stage. However, it can be seen that the weight The weight
of of specimensconcrete
cast-in-situ increasedexperienced
quickly at the earlysignificant
more stage, thenchanges
became stable
duringortheeven began to immersion.
12-month decrease after The
the sixth month, especially for specimens immersed in 10% sulfate solution (shown in Figure 5c).
weight of specimens increased quickly at the early stage, then became stable or even began to
decrease after the sixth month, especially for specimens immersed in 10% sulfate solution (shown in
Figure 5c).
Materials 2020, 13, 3179 11 of 17
Materials 2020, 13, x FOR PEER REVIEW 11 of 17

0.05
CCK PCK
C3S P3S
0.04
C5S P5S
C10S P10S

Weight change ratio

0.03

0.02

0.01

0.00
0 2 4 6 8 10 12
Time (Month)
(a)
0.05
CCK PCK
C3S P3S
0.04 C5S P5S
C10S P10S
Weight change ratio

0.03

0.02

0.01

0.00
0 2 4 6 8 10 12
Time (Month)
(b)
0.05
CCK PCK
C3S P3S
0.04 C5S P5S
C10S P10S
Weight change ratio

0.03

0.02

0.01

0.00
0 2 4 6 8 10 12
Time (Month)
(c)
Figure
Figure 5. Weightchange
5. Weight changeratios
ratiosfor
forconcrete
concretewith
with different
different water/cement
water/cement ratios:
ratios: (a) 0.40,
(a) 0.40, (b) 0.48,
(b) 0.48, and
and (c) 0.55.
(c) 0.55.

To give a clear comparison of degradation between the precast and cast-in-situ concrete, the
photos of the exposed surface of specimens after immersion are shown together. The image in Figure
Materials 2020, 13, 3179 12 of 17

Materials 2020, 13, x FOR PEER REVIEW 12 of 17

To give a clear comparison of degradation between the precast and cast-in-situ concrete, the photos
of the
6a showsexposed surface of
the exposed specimens
surface of theafter immersion
precast concretearewith
shown together. Theratio
a water/cement image ofin0.48
Figure 6a shows
immersed in
athe10%
exposed surface
sulfate of theThe
solution. precast concrete
images with a6b,c
in Figure water/cement
show theratio of 0.48
exposed immersed
surfaces in a 10%
of the sulfate
cast-in-situ
solution. The
concrete images in
immersed in Figure 6b,c show
10% sulfate the exposed
solutions, whilesurfaces of the cast-in-situ
the water/cement ratiosconcrete
are 0.48 immersed
and 0.55,in
10% sulfate solutions, while the water/cement ratios are 0.48 and 0.55, respectively.
respectively. The comparison distinctly shows that more potential cracks were generated on the The comparison
distinctlysurface
exposed shows of that more potential
cast-in-situ cracks
concrete. were generated
Moreover, there was on clearly
the exposed
more surface
shedding of of
cast-in-situ
concrete
concrete. Moreover, there was clearly more shedding of concrete powder
powder and fragments on the cast-in-situ concrete surface. The appearance comparison illustrates and fragments on the
cast-in-situ
that precastconcrete
concretesurface. The appearance
has a better comparison illustrates
resistance performance that precast
against sulfate attack concrete
than thathas of acast-in-
better
resistance performance against sulfate attack than that of cast-in-situ concrete. Additionally,
situ concrete. Additionally, the results illustrate that concrete with a low water/cement ratio clearly the results
illustrate
suffers that
less concrete with
degradation anda shows
low water/cement ratio clearly
a better performance sufferssulfate
against less degradation and shows
attack compared to thea
better performance
sample with a high against sulfateratio.
water/cement attack compared to the sample with a high water/cement ratio.

(a) (b) (c)

Figure 6. Surface
Surface photos
photosofofspecimens
specimenswith
with different
different water/cement
water/cement ratios:
ratios: (a) 0.40,
(a) 0.40, (b) 0.48,
(b) 0.48, and0.55.
and (c) (c)
0.55.
It is clear that the diameter and weight of concrete samples are significantly affected by sulfate
attack.
It isInclear
the that
earlythe
corrosion
diameterstage, sulfatesofpenetrates
and weight internalare
concrete samples concrete and reacts
significantly withbyconcrete
affected sulfate
composition
attack. In thetoearly
generate ettringite
corrosion andsulfates
stage, gypsum. The corrosion
penetrates products
internal are and
concrete accumulated in the
reacts with initial
concrete
cracks and pores
composition with immersion
to generate ettringite andtime. Soon after,
gypsum. The the initial products
corrosion cracks areare fully filled by the
accumulated in corrosion
the initial
products,
cracks andand excessive
pores pressure is time.
with immersion loaded on the
Soon walls
after, theofinitial
crackscracks
and pores to cause
are fully filledvolume
by theexpansion.
corrosion
During thisand
products, stage, the diameter
excessive pressureandisweight
loaded of specimens
on the walls increase with and
of cracks immersion
pores time, while
to cause in the
volume
expansion. During this stage, the diameter and weight of specimens increase with immersion of
later corrosion stage, the excessive filling of corrosion products loads great pressure on the walls the
time,
crack, in
while causing the corrosion
the later extending stage,
of initial
thecracks and generation
excessive of new cracks.
filling of corrosion products Moreover, the development
loads great pressure on
of awalls
the crackof system on the
the crack, concrete
causing thesurface
extending causes serious
of initial spalling
cracks andand shedding
generation ofof
new concrete
cracks.powder
Moreover,and
fragments, which cause a decrease of both the diameter and weight of concrete
the development of a crack system on the concrete surface causes serious spalling and shedding of specimens. Therefore,
the diameter
concrete powder of concrete specimens
and fragments, which is acause
comprehensive
a decrease of result
bothof the
the increaseand
diameter tendency
weightinduced
of concreteby
the proceeding
specimens. of expansion
Therefore, and theofdecrease
the diameter concretetendency
specimens induced by the falling result
is a comprehensive off of concrete on the
of the increase
exposed surface.
tendency inducedThe by weight of concrete
the proceeding specimens and
of expansion is a comprehensive result ofinduced
the decrease tendency the increase tendency
by the falling
induced
off by theon
of concrete accumulation
the exposed of sulfateThe
surface. corrosion
weight products
of concrete and the decrease
specimens tendency induced
is a comprehensive by
result
the shedding of concrete fragments. Furthermore, the diameter and weight
of the increase tendency induced by the accumulation of sulfate corrosion products and the decrease of specimens are mainly
controlledinduced
tendency by the increase tendency of
by the shedding in concrete
the earlyfragments.
corrosion stage, while in the diameter
Furthermore, later stage, theweight
and decreaseof
tendency plays
specimens the leading
are mainly role. Hence
controlled by theboth the diameter
increase tendency and inweight of concrete
the early corrosion specimens encounter
stage, while in the
a rapid
later decrease
stage, at the end
the decrease of the immersion,
tendency especially
plays the leading forHence
role. concrete with
both thea diameter
high water/cement
and weight ratio
of
immersed
concrete in the solution
specimens encounterwithaarapid
high decrease
sulfate concentration
at the end of (such as the specimen
the immersion, especiallyC10Sforshown
concretein
with a high water/cement ratio immersed in the solution with a high sulfate concentration (such as
the specimen C10S shown in Figures 4c and 5c). From the results, it can be inferred that cast-in-situ
concrete suffered more severe degradation in the later corrosion stage than precast concrete. In
Materials 2020, 13, 3179 13 of 17

Figures 4c and 5c). From the results, it can be inferred that cast-in-situ concrete suffered more severe
degradation in the later corrosion stage than precast concrete. In addition, the spalling and shedding
of concrete fragments became more serious at the later stage, which damaged the integrity of the outer
layer of concrete and then caused potential loss of concrete strength.

3.4. Mechanical Properties

The results of compressive strength tests are presented in Figure 7. It is clear that the strength of
different specimens in different solutions is quite different.
Materials
For2020, 13, x FOR
precast PEER REVIEW
concrete specimens, the strength showed a relatively stable increase tendency during13 of 17

the immersion, especially for concrete specimens immersed in 3% and 5% sulfate solutions. For concrete
addition, the spalling and shedding of concrete fragments became more serious at the later stage,
immersed in 10% sulfate solution (with water/cement ratio of 0.55), the strength began to decrease after
which damaged the integrity of the outer layer of concrete and then caused potential loss of concrete
the ninth month, while for concrete specimens with water/cement ratios of 0.40 and 0.48, the strength
strength.
remained increasing or stable even at the end of the immersion.
It is noteworthy that the strength of cast-in-situ concrete increased quickly, and the value was
3.4. Mechanical Properties
relatively low in the early stage, while after that, the increase tendency of strength became stable or
evenThebeganresults of compressive
to decrease after thestrength tests are
sixth month. In presented in Figure
addition, one could7.notice
It is clear
thatthat the strength
concrete lost moreof
different specimens in different
strength when immersed in the solutions is quite different.
with higher sulfate concentration.

65
CCK PCK
C3S P3S
60
C5S P5S
Compressive Strength (MPa)

C10S P10S
55

50

45

40

35
0 2 4 6 8 10 12
Time (Months)
(a)
55
CCK PCK
C3S P3S
50
C5S P5S
Compressive Strength (MPa)

C10S P10S
45

40

35

30

25
0 2 4 6 8 10 12
Time (Months)
(b)
Figure 7. Cont.
Materials 2020, 13, 3179 14 of 17
Materials 2020, 13, x FOR PEER REVIEW 14 of 17

55
CCK PCK
50
C3S P3S
C5S P5S

Compressive Strength (MPa)

45
C10S P10S
40

35

30

25

20

15
0 2 4 6 8 10 12
Time (Months)
(c)
Figure Compressivestrength
Figure 7. Compressive strengthofofconcrete
concrete with
with different
different water/cement
water/cement ratios:
ratios: (a) 0.40,
(a) 0.40, (b) 0.48,
(b) 0.48, and
and (c) 0.55.
(c) 0.55.

It
Foris precast
clearly illustrated in Figure the
concrete specimens, 7 that the water/cement
strength ratio had
showed a relatively a significant
stable influence during
increase tendency on the
strength
the immersion, especially for concrete specimens immersed in 3% and 5% sulfate solutions.ratio
of concrete specimens. Generally, the strength of concrete with a greater water/cement For
was clearly
concrete lower than
immersed in the
10%strength of concrete
sulfate solution withwater/cement
(with a lower water/cement ratio. the
ratio of 0.55), Moreover,
strengththe results
began to
distinctly indicated that the strength of concrete with a higher
decrease after the ninth month, while for concrete specimens with water/cement ratios of 0.40 andwater/cement ratio began to decrease
earlier,
0.48, theand the strength
strength remained wasincreasing
relatively or low at the
stable endatofthe
even theendimmersion. In addition, the strength of
of the immersion.
concrete
It is in the solution
noteworthy with
that theastrength
higher sulfate concentration
of cast-in-situ concrete decreased
increased faster
quickly,and lost
and more strength
the value was
after immersion.
relatively low in the early stage, while after that, the increase tendency of strength became stable or
evenFor beganprecast concreteafter
to decrease specimens,
the sixth themonth.
hardening process and
In addition, one strength
could notice development
that concrete werelost finished
more
before being put into the sulfate solutions. Thus,
strength when immersed in the solutions with higher sulfate concentration. sulfate ions had to penetrate internal concrete from
the outside-in
It is clearly illustrated in Figure 7 that the water/cement ratio had a significant influence onwith
with immersion time. Sulfate ions penetrated the outer layer of concrete together the
the permeating
strength of concreteof pore water during
specimens. the immersion.
Generally, the strength Then, the penetrated
of concrete sulfatewater/cement
with a greater ions reacted with ratio
the
wasconcrete
clearly lowercomposition
than thetostrength
generate ofcorrosion
concrete with products,
a lowerwhich accumulated
water/cement ratio. in Moreover,
the initial cracks and
the results
pores to cause expansion and degradation. Therefore, the degradation
distinctly indicated that the strength of concrete with a higher water/cement ratio began to decrease of precast concrete proceeded
from
earlier,theand
surface into the was
the strength internal areas of
relatively low theatconcrete
the end of gradually. However,
the immersion. for cast-in-situ
In addition, concrete,
the strength of
the strength development of concrete was negatively affected in
concrete in the solution with a higher sulfate concentration decreased faster and lost more strength the early corrosion stage, since the
hardening
after immersion.process of concrete was not complete during this stage. Hence, the strength of cast-in-situ
concrete
For was
precastlower than that
concrete of precastthe
specimens, concrete,
hardening evenprocess
when the andspecimens were immersed
strength development in the
were same
finished
sulfate solutions, especially when the sulfate concentration was high.
before being put into the sulfate solutions. Thus, sulfate ions had to penetrate internal concrete from
It has to be
the outside-in emphasized
with immersion that theSulfate
time. water/cement ratio hasthe
ions penetrated a significant
outer layereffect on the together
of concrete strengthwith and
resistance performance of concrete against sulfate attack. It is
the permeating of pore water during the immersion. Then, the penetrated sulfate ions reacted with well accepted that concrete with a
lower water/cement ratio always results in a relatively higher density
the concrete composition to generate corrosion products, which accumulated in the initial cracks and and lower porosity. Therefore,
the
poresstrength
to cause of expansion
specimensand withdegradation.
lower water/cement Therefore, ratio
the is relatively high.
degradation In addition,
of precast concrete the porosity
proceeded
of concrete also plays a significant role in affecting the diffusion speed
from the surface into the internal areas of the concrete gradually. However, for cast-in-situ concrete, of sulfate ions, subsequently
influencing
the strengththe mechanicalof
development property
concreteofwas concrete.
negatively affected in the early corrosion stage, since the
hardening process of concrete was not complete corrosion
The generation and accumulation of sulfate during this products in the cracks
stage. Hence, and pores
the strength influence
of cast-in-situ
the properties of concrete. In the very early corrosion stage,
concrete was lower than that of precast concrete, even when the specimens were immersed in the cracks and pores are not fully filled;
the
hence, the accumulation
same sulfate of corrosion
solutions, especially products
when do notconcentration
the sulfate affect the strength was of concrete. Then, the excessive
high.
fillingItof corrosion
has products generate
to be emphasized that the pressure
water/cement on theratio
wallshasofainternal
significantcrackseffectandonpores, making and
the strength the
concrete denser and causing a slight increase in strength. Then, initial
resistance performance of concrete against sulfate attack. It is well accepted that concrete with a lower cracks are extended and new
cracks are generated,
water/cement decreasing
ratio always resultstheinstrength
a relatively of concrete
higher to a largeand
density extent.
lower In porosity.
this regard, for concrete
Therefore, the
with a higher water/cement ratio, it takes less time for sulfates to
strength of specimens with lower water/cement ratio is relatively high. In addition, the porosity of penetrate internal concrete regions
and brings
concrete a great
also plays deal of damage role
a significant to concrete
in affectingstructures. Moreover,
the diffusion speedthe tensile
of sulfate strength
ions, of the internal
subsequently
influencing the mechanical property of concrete.
Materials 2020, 13, 3179 15 of 17

concrete area with a higher water/cement ratio is low, making it easier for sulfate corrosion products to
generate new cracks and bring great damage.

4. Conclusions
Experiments were performed to investigate the degradation of precast and cast-in-situ concrete
caused by sulfate attack. Parameters regarding physical, chemical, and mechanical properties were
determined and compared in detail. Methods of SEM, EDS, and XRD were used to reveal the
micro-structural and mineral changes after immersion. Based on the experiments in the present study,
the main conclusions are as follows:
Degradation of both precast and cast-in-situ concrete is caused by chemical sulfate attack when
the concrete is fully immersed in the sulfate-rich environments. The main corrosion products induced
by sulfate attack are ettringite and gypsum.
Sulfate attack results in great expansion and weight loss in the later corrosion stage, putting
concrete structures in great danger, especially for cast-in-situ concrete structures. The diffusion of
sulfates is faster in cast-in-situ concrete than that in the precast concrete due to the faster development
of cracks in the cast-in-situ concrete.
The faster strength increase of cast-in-situ concrete in the early corrosion stage is induced by
the faster accumulation of corrosion products. Cast-in-situ concrete obviously suffers more strength
loss during corrosion. Precast concrete has better resistance performance against sulfate attack
than cast-in-situ concrete structures, indicating that precast concrete structures are more suitable in
sulfate-rich environments.

Author Contributions: Conceptualization, G.Z. and M.S.; methodology, G.Z. and H.F.; software, M.G.; validation,
G.Z.; formal analysis, M.S.; investigation, M.G. and H.F.; resources, G.Z.; data curation, M.G.; writing—original
draft preparation, G.Z.; writing—review and editing, M.S.; visualization, G.Z.; supervision, G.Z.; project
administration, G.Z.; funding acquisition, G.Z. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China, grant number 51908466;
the Post-Doctoral Innovative Talent Support Program, grant number BX20200287; the Fundamental Research
Funds for the Central Universities, CHD, grant number 300102210305; and the Natural Science Foundation of
Shaanxi Province, grant numbers 2020JQ-361 and 2020JQ-271.
Acknowledgments: The authors would like to thank Longfei Xu (in Chang’an University) for giving us technical
support during the experiments.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Ouyang, C.; Nanni, A.; Chang, W.F. Internal and external sources of sulfate ions in Portland cement mortar:
Two types of chemical attack. Cem. Concr. Res. 1988, 18, 699–709. [CrossRef]
2. Jiang, X.; Zhang, Y.; Xiao, R.; Polaczyk, P.; Zhang, M.; Hu, W.; Bai, Y.; Huang, B. A Comparative Study
on Geopolymers Synthesized by Different Classes of Fly Ash after Exposure to Elevated Temperatures.
J. Clean. Prod. 2020, 37, 1583–1589. [CrossRef]
3. Zhao, G.; Li, J. Study on degradation in axial bearing capacity of a cast-in-situ pile caused by sulfate attack in
saline area. In Proceedings of the GeoShanghai International Conference, Shanghai, China, 26–29 May 2018;
pp. 253–264.
4. Jiang, X.; Xiao, R.; Zhang, M.; Hu, W.; Bai, Y.; Huang, B. A laboratory investigation of steel to fly ash-based
geopolymer paste bonding behavior after exposure to elevated temperatures. Constr. Build. Mater. 2020, 254,
119267. [CrossRef]
5. Cohen, M.D.; Mather, B. Sulfate attack on concrete: Research needs. Mater. J. 1991, 88, 62–69.
6. Tan, L.; Wang, F.; Liang, M.; Wang, X.; Das, R.; Mao, D.; Luo, Y. Antibiotic resistance genes attenuated with
salt accumulation in saline soil. J. Hazard. Mater. 2019, 374, 35–42. [CrossRef]
7. Wang, X.; Xue, Z.; Lu, X.; Liu, Y.; Liu, G.; Wu, Z. Salt leaching of heavy coastal saline silty soil by controlling
the soil matric potential. Soil. Water. Res. 2019, 14, 132–137. [CrossRef]
Materials 2020, 13, 3179 16 of 17

8. Cardon, G.E.; Davis, J.G.; Bauder, T.A.; Waskom, R.M. Managing Saline Soils; Colorado State University
Cooperative Extension: Fort Collins, CO, USA, 2003.
9. Gu, Y.; Martin, R.P.; Metalssi, O.O.; Fen-Chong, T.; Dangla, P. Pore size analyses of cement paste exposed to
external sulfate attack and delayed ettringite formation. Cem. Concr. Res. 2019, 123, 105766. [CrossRef]
10. Wang, Z.; Yu, J.; Li, G.; Zhang, M.; Leung, C.K. Corrosion behavior of steel rebar embedded in hybrid
CNTs-OH/polyvinyl alcohol modified concrete under accelerated chloride attack. Cem. Concr. Compos. 2019,
100, 120–129. [CrossRef]
11. Aziez, M.N.; Bezzar, A. Effect of temperature and type of sand on the magnesium sulphate attack in sulphate
resisting Portland cement mortars. J. Adhes. Sci. Technol. 2018, 32, 272–290. [CrossRef]
12. Ragoug, R.; Metalssi, O.O.; Barberon, F.; Torrenti, J.M.; Roussel, N.; Divet, L.; Lacaillerie, J.B.D.E. Durability of
cement pastes exposed to external sulfate attack and leaching: Physical and chemical aspects. Cem. Concr. Res.
2019, 116, 134–145. [CrossRef]
13. Zhao, G.; Li, J.; Han, F.; Shi, M.; Fan, H. Sulfate-induced degradation of cast-in-situ concrete influenced by
magnesium. Constr. Build. Mater. 2019, 199, 194–206. [CrossRef]
14. Neville, A. The confused world of sulfate attack on concrete. Cem. Concr. Res. 2004, 34, 1275–1296. [CrossRef]
15. Li, J.; Shi, G.Z.M. Degradation and life prediction model for piles due to crystallization attack in saline area.
Adv. Cem. Res. 2018, 30, 1–15.
16. Du, J.; Li, G.; Wu, J. Concrete sulfate corrosion coupled with hydraulic pressure. Mar. Georesour. Geotec. 2020,
38, 40–47. [CrossRef]
17. Prasad, B.K.R. Fracture Mechanics of Concrete; Wiley: New York, NY, USA, 1995.
18. Horkoss, S.; Julien, S.; Escadeillas, G.; Lteif, R.; Rizk, T. Influence of clinker sulfate on cement paste external
sulfate attack. Adv. Cem. Res. 2013, 25, 217–224. [CrossRef]
19. Zhao, G.; Shi, M.; Fan, H.; Cui, J.; Xie, F. The influence of multiple combined chemical attack on cast-in-situ
concrete: Deformation, mechanical development and mechanisms. Constr. Build. Mater. 2020, 251, 118988.
[CrossRef]
20. Zhao, G.; Li, J.; Shi, M.; Fan, H.; Cui, J. Degradation mechanisms of cast-in-situ concrete subjected to
internal-external combined sulfate attack. Constr. Build. Mater. 2020, 248, 118683. [CrossRef]
21. Karakoç, M.B.; Türkmen, İ.; Maraş, M.M.; Kantarci, F.; Demirboğa, R. Sulfate resistance of ferrochrome slag
based geopolymer concrete. Ceram. Int. 2016, 42, 1254–1260. [CrossRef]
22. Liu, F.; You, Z.; Diab, A.; Liu, Z.; Zhang, C.; Guo, S. External sulfate attack on concrete under combined effects
of flexural fatigue loading and drying-wetting cycles. Constr. Build. Mater. 2020, 249, 118224. [CrossRef]
23. Ikumi, T.; Segura, I. Numerical assessment of external sulfate attack in concrete structures. A review.
Cem. Concr. Res. 2019, 121, 91–105. [CrossRef]
24. Li, J.; Xie, F.; Zhao, G.; Li, L. Experimental and numerical investigation of cast-in-situ concrete under external
sulfate attack and drying-wetting cycles. Constr. Build. Mater. 2020, 249, 118789. [CrossRef]
25. He, R.; Zheng, S.; Gan, V.J.; Wang, Z.; Fang, J.; Shao, Y. Damage mechanism and interfacial transition zone
characteristics of concrete under sulfate erosion and Dry-Wet cycles. Constr. Build. Mater. 2020, 255, 119340.
[CrossRef]
26. Tian, B.; Cohen, M.D. Does gypsum formation during sulfate attack on concrete lead to expansion?
Cem. Concr. Res. 2020, 30, 117–123. [CrossRef]
27. Zhang, H.; Ji, T.; Liu, H. Performance evolution of recycled aggregate concrete (RAC) exposed to external
sulfate attacks under full-soaking and dry-wet cycling conditions. Constr. Build. Mater. 2020, 248, 118675.
[CrossRef]
28. Bonen, D.; Cohen, M.D. Magnesium sulfate attack on Portland cement paste: I. Microstructural analysis.
Cem. Concr. Res. 1992, 22, 169–180. [CrossRef]
29. Basista, M.; Weglewski, W. Chemically assisted damage of concrete: A model of expansion under external
sulfate attack. Int. J. Damage Mech. 2009, 18, 155–175. [CrossRef]
30. Santhanam, M. Studies on Sulfate Attack: Mechanisms, Test Methods, and Modeling. Ph.D. Thesis, Purdue
University, West Lafayette, IN, USA, August 2001.
31. Tan, Y.; Yu, H.; Ma, H.; Zhang, Y.; Wu, C. Study on the micro-crack evolution of concrete subjected to stress
corrosion and magnesium sulfate. Constr. Build. Mater. 2017, 141, 453–460. [CrossRef]
32. CBMA (China Building Materials Academy). GB175-2007: Common Portland Cements; Standards Press of
China: Beijing, China, 2007. (In Chinese)
Materials 2020, 13, 3179 17 of 17

33. ASTM. Standard Specification for Portland Cement, ASTM Standard C150-07; American Society for Testing and
Materials: West Conshohocken, AL, USA, 2007.
34. Sun, C.; Chen, J.; Zhu, J.; Zhang, M.; Ye, J. A new diffusion model of sulfate ions in concrete. Constr. Build. Mater.
2013, 39, 39–45. [CrossRef]
35. Ikumi, T.; Cavalaro, S.H.; Segura, I.; Aguado, A. Alternative methodology to consider damage and expansions
in external sulfate attack modeling. Cem. Concr. Res. 2014, 63, 105–116. [CrossRef]
36. Geng, J.; Easterbrook, D.; Li, L.Y.; Mo, L.W. The stability of bound chlorides in cement paste with sulfate
attack. Cem. Concr. Res. 2015, 68, 211–222. [CrossRef]
37. William, G.H.; Bryant, M. “Sulfate attack,” or is it? Cem. Concr. Res. 1999, 29, 789–791.

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