Construction and Building Materials 204 (2019) 265–275

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Construction and Building Materials

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Effects of sulfate and magnesium ion on the chloride transportation

behavior and binding capacity of Portland cement mortar
Shukai Cheng a, Zhonghe Shui a, Tao Sun a,b,c,⇑, Xu Gao c, Cheng Guo a
a
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China
b
Key Laboratory of Roadway Bridge & Structure Engineering, Wuhan University of Technology, Wuhan 430070, China
c
School of Civil Engineering and Architecture, Wuhan University of Technology, Wuhan 430070, China

h i g h l i g h t s

Nine mortar mixtures with different w/b ratios and SCMs were prepared and exposed to four solutions, respectively.

Chloride transport behaviors and binding capacity in various cementitious systems were studied.

Corrosion products of mortar samples were identified by XRD and TG-DSC.

The presence of sulfate ion increased the chloride binding capacity, while the magnesium and sulfate + magnesium ion declined the chloride binding
capacity in chloride solution.

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

Article history: The chloride diffusion induced reinforcement corrosion seriously threatens the durability of concrete
Received 24 October 2018 construction in marine environments. This paper investigates the effects of sulfate and magnesium ion
Received in revised form 7 December 2018 in simulated seawater on the chloride transportation behavior and binding capacity of Portland cement
Accepted 22 January 2019
mortar with and without fly ash (FA) and ground blast furnace slag (BFS). Chloride ion transport profile,
binding capacity and corrosion products of mortar specimens exposed to NaCl, NaCl + MgCl2, NaCl
+ Na2SO4 and NaCl + MgCl2 + Na2SO4 solutions at different penetration depths were conducted respec-
Keywords:
tively. Results indicate that the samples exposed to NaCl + MgCl2 solutions show the highest chloride
Marine environment
Sulfate ion
content at the outmost layer (0–5 mm). The presence of magnesium ion and combined sulfate and mag-
Magnesium ion nesium ion in chloride salt accelerates chloride ingress and increase apparent chloride diffusion coeffi-
Chloride binding cient, while reduces the content of calcium hydroxide thus results in a reduction of the chloride
Friedel’s salt (Fs) binding. However, the sulfate ion in NaCl + Na2SO4 solutions inhibits the chloride diffusion, enhances
bound chloride and refined the pore size due to the formation of Friedel’s salt (Fs) with chloride ion.
Furthermore, the addition of BFS significantly improves the resistance to chloride ingress into mortar
specimens.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
It is well known that the reinforcement corrosion induced by
chloride ion is one of the most major durability problems of the
concrete structure in many reports [1–10]. The chloride ion trans-
ports to the inner of concrete and decrease the alkalinity of pore
solution, which causes deactivation and corrosion of reinforcement
steel in concrete. Actually, the deactivation and corrosion of rein-
forcement steel in concrete are mainly induced by the free chloride
⇑ Corresponding author at: Key Laboratory of Roadway Bridge & Structure
Engineering, Wuhan University of Technology, Wuhan 430070, China.
E-mail address: sunt@whut.edu.cn (T. Sun).
ion. While the bound chloride ion can react with some aluminate
phase and form the Friedel’s salt (Fs), which change both the inter-
nal pore structure and the free chloride ions concentration in the
pore solution [11]. Thus, reducing the free chloride ion content
by increasing the bound chloride ion content will be contributed
to durability improvements in concrete structures. However, many
factors such as the chloride ion concentration [12,13], supplemen-
tary cementitious materials (SCMs) [14–17],chemical erosion asso-
ciated with chloride ion [18–20], and alkalinity of pore solution
[21,22] will affect the chloride binding capacity of concrete.
Chloride and sulfate ion are existed concomitantly in marine
environment, which may cause diversified construction damages
due to reinforcement corrosion and sulfate attack [23–26], or even

https://doi.org/10.1016/j.conbuildmat.2019.01.132
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
266 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275

a combined attack of both [27–31]. Jin et al. [32] reported that the Table 2
presence of sulfate ions in a combined solutions of 5% Na2SO4 and Chemical compositions of Portland cement clinker, fly ash and blast furnace slag used,
as determined by XRF and Blaine surface areas.
3.5% NaCl decreased the chlorides ingress in concrete at early
exposure period, while increased chloride penetration at the latter Oxide (%) Cement clinker Fly ash Blast furnace salg
exposure period. Similarly, a study concluded that the penetration SiO2 21.76 47.88 34.36
of free chloride ions for ordinary Portland cement concrete and Al2O3 5.83 37.32 14.64
blast-furnace slag cement concrete was increased when the CaO 62.69 3.78 38.86
MgO 1.72 0.51 7.81
sodium sulfate existed in sodium chloride solution [33]. Weerdt Fe2O3 3.41 4.12 0.30
et al. [34] suggested that the sulfate ion in seawater decreased SO3 1.09 1.10 2.11
the chloride binding and resulted in part of AFm phases converted K2O 1.22 0.67 0.37
to ettringite. Moreover, some studies revealed that the stability of Na2O 0.07 0.22 0.24
LOI 1.11 2.66 0.79
bound chloride ions solution was susceptible to sulfate salt attack
Blaine fineness (m2/kg) 376 366 435
[35], which caused part of the chloride ion of Friedel’s salt (Fs) Density (kg/m3) 3150 2280 2950
replaced by sulfate salt [36]. Therefore, sulfate salt has significant
influences on the chloride perpetration and binding capacity.
Additionally, magnesium and chloride salts are also coexisting
in seawater. Previous researches showed that, in contrast to NaCl
solution, the magnesium ion in chloride solution increased the
chloride binding in cement paste [20]. The reason was mentioned
that magnesium reacted with hydroxyl ions to form brucite and
led to a lower pH, which was one of the major parameters influenc-
ing chloride binding. Thermodynamic model was concluded that
the precipitation of Mg(OH)2 reduced the pH and a consequent
increase in the solubility of Ca, which resulted in higher chloride
content [37]. Hence, chloride binding of concrete exposed to chlo-
ride and magnesium environment is mainly depended on the con-
centration of magnesium ion associated with chloride salts. The
chloride ion induced reinforcement corrosion, sulfate and magne-
sium salt attack appear together in the marine environment and
deterioration mechanisms occur simultaneously such as
chlorides-sulfate, chlorides-magnesium and chlorides-sulfate-
magnesium combined attacks [38–40]. However, by far, investiga-
tions regarding the effect mechanism of sulfate and magnesium Fig. 1. Particle size distribution of raw materials.
ion in marine environment on the chloride transport properties
and binding capacity are insufficient and need further study.
This paper is to reveal the effects of sulfate, magnesium and sul- (FA) and granulated blast-furnace slag (BFS) were supplied by
fate + magnesium ion on the chloride transport and binding capac- Wuhan Iron Group. Table 2 showed the chemical compositions
ity in Portland cement mortar exposed to four different solutions and specific surface areas of the raw materials, whose was deter-
(NaCl, NaCl + Na2SO4, NaCl + MgCl2 NaCl + MgCl2 + Na2SO4). The mined with X-ray fluorescence (XRF) and the Blaine method,
incorporating of SCMs can not only improve the chloride binding respectively. The particle size distribution (PSD) of the raw materi-
capacity, but also the increase the resistance to sulfate attack of als was shown in Fig. 1 by using Malvern Mastersizer 2000 laser
concrete. Therefore, chloride transport resistance capacity and diffraction. The analytical reagents including sodium chloride, hex-
chloride binding capacity of hydrated cement mortar with and ahydrate magnesium chloride and anhydrous sodium sulfate were
without SCMs exposed to different simulated solutions are studied. utilized to simulate the major element of seawater. Table 3 showed
Additionally, the evolution of corrosion products is represented by the detailed compositions of the simulated solutions and a com-
X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The parison of simulated solutions and seawater.
pore structure developments of exposed samples are analyzed by
mercury intrusion porosimetry (MIP). 2.2. Sample preparations

2. Materials and methods According to Chinese standard of Test methods of physical

property for dry-mix mortar (GB/T 29756-2013), mortar mixtures
2.1. Materials with a series of water to binder ratio (0.4, 0.45 and 0.5) and a con-
stant sand to binder ratio (sand/binder = 3) were prepared. Table 4
The cement clinker was obtained from Huaxin Cement Co., Ltd. showed the detailed preparation of mortar samples. 30 wt% and
Its mineral compositions were presented in Table 1. Grade II fly ash 50 wt% of the cement was respectively partially replaced with FA
and BFS. Fig. 2 illustrated the sketch of the procedure of the exper-
iment. Firstly, all mortar mixtures were casted with size of
Table 1 40 mm  40 mm  160 mm. The mortar specimens were
Mineral compositions of cement clinker.
immersed in pure water for 3 days and then cured at a standard
Mineral composition wt% curing condition (temperature of 20 ± 2 °C and relative humidity
C3S 47.48 of 98 ± 2%) for the following 4 days. Then, all samples were dried
C2S 26.65 and its four rectangular surfaces were sealed by epoxy resin except
C3A 9.69 two 40 mm  40 mm exposure surfaces. Afterwards, all samples
C4AF 10.37 were diverted to cover plastic container and immersed in the expo-

1.85
CS sure solutions for 60 days at the temperature of 20 ± 2 °C. In order
to maintain concentration stability of all kinds of ions, exposed
 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275 267

Table 3
Concentration of exposed solutions used in the experiment.

Concentration of exposed solutions Total chloride ion Total sulfate ion Total magnesium ion Major elements in seawater
(mol/L) (mol/L) (mol/L) (mol/L)
0.56 mol/L NaCl 0.56 – – 0.546
0.56 mol/L NaCl + 0.028 mol/L Na2SO4 0.56 0.28 – 0.028
0.448 mol/L NaCl + 0.056 mol/L MgCl2 0.56 – 0.056 0.056
0.448 mol/L NaCl + 0.056 mol/L MgCl2 + 0.028 mol/L 0.56 0.28 0.056 0.63
Na2SO4

Table 4
Sample composition designs of exposed mortar.

Samples Clinker (g) BFS (g) FA (g) Sand (g) Water (g) w/b SCM
CM 450 – – 1350 180 0.4 –
CM + BFS 225 225 – 1350 180 50 wt% BFS
CM + FA 360 – 90 1350 180 30 wt% BFS
CM 450 – – 1350 202.5 0.45 –
CM + BFS 225 225 – 1350 202.5 50 wt% BFS
CM + FA 360 – 90 1350 202.5 30 wt% BFS
CM 450 – – 1350 225 0.5 –
CM + BFS 225 225 – 1350 225 50 wt% BFS
CM + FA 360 – 90 1350 225 30 wt% BFS

Mortar preparation

3 days water curing + 4 days standard curing

Four rectangular surfaces were sealed

and the other surfaces were exposed

Mortar samples were

Phase compositions immersed in different Grinding powder
exposure solution for 60 days

X-ray diffraction Total chloride content

Thermo gravimetric Free chloride content
NaCl
NaCl+MgCl2
NaCl+Na2SO4
NaCl+Na2SO4+MgCl2

Fig. 2. Sketch of the procedure of the experiment.

solutions were replaced every two weeks. Eventually, one of the
exposed surfaces in all samples was used for profile grinding
according to the following depths: 0–5 mm, 5–10 mm, 10–
15 mm and 15–20 mm. The collected powder was passed through
a sieve of 0.15 mm and then stored in sealed plastic bags.
2.3. Methods
2.3.1. Chloride ion profiles
According to the Chinese standard of Technical specification for
test of chloride ion content in concrete (JGJ/T 322-2013), the free
and total chloride ion contents of mortar samples were respec-
tively measured. The water-soluble chloride ion, namely the free
chloride ion was conducted based on the following procedure.
5 g of powder collected from each section was dissolved in 50 mL
deionized water, vibrated for 1–2 min and then stored for 24 h.
The above solution was filtered using funnel and assimilated the
supernatant of 10 mL by pipette, which was titrated with
0.02 mol/L silver nitrate solution. The free chloride content (Cf )
of mortar samples was calculated by Eq. (1).
C  V 3  0:3545
Cf ¼  100% ð1Þ
G  VV 21
268 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275

where C denoted the concentration of silver nitrate solution, mol/L; ðC  V  C K  V 1 Þ  0:3545

Ct ¼  100% ð2Þ
V3 represented the consumed volume of silver nitrate solution at G  VV 23
each test, mL; G was the sample mass of exposed mortar; V2 and
V1 was the volume of water-soluble specimens and the volume of where C and CK were the concentration of silver nitrate solution and
titrated solution, respectively. potassium thiocyanate solution, mol/L; V and V1 respectively
Additionally, the acid-soluble chloride ion, namely the total denoted the volume of the added silver nitrate solution and the con-
chloride content (Ct ) was recorded according to the following pro- sumed volume of potassium thiocyanate solution at each test, mL;
cedure. 5 g of collected powder was dissolved in 50 mL diluted G was the sample mass of exposed mortar.
nitric acid (water: nitric acid = 15:85) and then was shocked for According to Ref. [41], chloride binding describes the relation-
1–2 min and stored for 24 h. Afterwards, 10 mL of supernatant liq- ship between free and total chlorides in mortars as following Eq.
uid was titrated with 0.02 mol/L potassium thiocyanate. The total (3).
chloride content was calculated by Eq. (2). C t ¼ aC f ð3Þ

Fig. 3. Total chloride content of different mortar binder in the exposure solutions. Fig. 4. Free chloride content of different mortar binder in the exposure solutions.
 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275 269

Based on Eqs. (1) and (2), the bound chloride content (Cb ) and with BFS and FA have different influences on the chloride ion pro-
chloride binding capacity could be determined by Eq. (4) files. It is observed that the CM100 samples show the highest total
and free chloride content at any depth except for the outmost layer
Cb ¼ Ct  Cf ð4Þ
(0–5 mm), while the CM50BFS50 exhibits the lowest total and free
Therefore, the chloride binding capacity can be calculated by Eq. chloride content. The results indicate that the mortar incorporating
(5). with 50 wt% BFS show the lowest chloride ingress. However, the
addition of FA seems have no obvious influence on the chloride
Cb
R¼ ¼a1 ð5Þ ion profiles due to its low pozzolanic reaction [44].
Lf

2.3.2. Chloride ion diffusion coefficient

In this case, chloride ion transportation can be simplified as one
dimensional diffusion through a semi-infinite medium. The Fick’s
second law of diffusion is commonly used to describe the chloride
diffusion into concrete [42]. The apparent chloride ion diffusion
coefficient is an important index which can be used to characterize
the speed of chloride ingress. The apparent chloride diffusion coef-
ficient and the concentration at the surface of the sample are deter-
mined by fitting experimental data using the solution of Fick’s
second law fitting Eq. (6).
  
x
C x;t ¼ C s 1  er f p2
ffiffiffiffiffiffiffiffi ð6Þ
Da t
where Cx; t is the total chloride content at depth x (m) and exposure
time t (s), Cs is the chloride content at the surface and Da is the
apparent diffusion coefficient. The chloride content at the surface
(Cs ) and apparent diffusion coefficient (Da ) are obtained from the
best fit by least squares.

2.3.3. Hydration products

1–2 g of collected powder at different penetration depths was
characterized by X-Ray diffraction (XRD), with a Bruker D8
Advance diffractometer using Cu Ka = 1.5406 Å. The scan was con-
ducted between position 5° and position 70°/2h, with an increment
of 0.019° and a measuring time 141.804 s/step. The acquired data
were analyzed using JADE 5.0.
The thermogravimetric analysis (TGA) was performed using a
Simultaneous Thermal Analysis (STA) STA2500. The specimens
were heated from 30 °C to 1000 °C at a rate of 10 °C/min under
an inert atmosphere with N2 flow of 30 mL/min. The weight loss
and temperature intervals of specimens were determined respec-
tively based on the thermogravimetric curves (TG) and derivative
thermogravimetric curves (DTG).

2.3.4. Pore structure characterization

The pore structure of exposed mortar samples is conducted by
using micromeritics mercury porosimeter (Auto Pore IV-9500).
The specimens (about 1–2 g) are cut from the exposed mortar
without the surface, then soaked in absolute ethyl alcohol and
dried in a vacuum atmosphere at 40 ± 2 °C for 12 h before testing.

3. Results and discussion

3.1. Chloride ion transport profiles

Figs. 3 and 4 illustrate the effects of w/b ratio and SCMs on the
chloride ion profiles. It is clear that, with the increasing of penetra-
tion depths, all mixtures exhibit a distinctly decrease of total and
free chloride content after 60 days of exposure. Obviously, total
and free chloride content in different binder mortar samples is ris-
ing accordingly with the increase of w/b ratio. This is in agreement
with previous studies suggested that the chloride content
increased with the increasing w/b ratio [12,43]. In addition, it is
found that the free chloride content in all samples show a similar Fig. 5. Apparent chloride diffusion of mortar samples with different w/b exposed to
behavior as the total chloride content. Replacements of cement simulated solutions (a) CM100; (b) CM50S50; (c) CM70F30.
270 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275

The effects of sulfate, magnesium ion and compound sulfate coefficient. The main reason can be attributed to the fineness and
and magnesium ion on the chloride ion profiles exposed to differ- secondary hydration reaction by BFS, which can improve the com-
ent simulated solutions are also depicted in Figs. 3 and 4. It is pactness and resistance to chloride penetration [14,41].
observed that, regardless of different binders, the chloride ingress
of mortar specimens exposed to NaCl + MgCl2 solutions is higher
3.3. Chloride binding capacity
than that the NaCl solution. For example, in cementitious systems
with w/b = 0.5, the specimens immersed in NaCl + MgCl2 solutions
The relationships between the free chloride content and total
seemingly show the highest total and free chloride content at the
chloride content in the cementitious systems with different w/b
depths of 0–5 mm. This is attributed to the associated cation type,
ratio and SCMs are summarized in Table 5. It is clear that the rela-
namely Mg2+ can react with Ca(OH)2, dissolve the protecting layer
tionships between free chloride content and total chloride content
and decline the pH value in the pore solution, thus accelerate the
in mortar provide a good fit at a chloride concentration of 0.56 M.
chloride ingress [20,37]. Moreover, the simultaneous exist of sul-
In addition, chloride binding capacity of mortar exposed to differ-
fate and magnesium ion results in increase of total chloride con-
ent solutions is presented in Fig. 6. It is also observed that there is
tent. This reason can be explained that magnesium ion reacts
an interaction between w/b and SCMs. For instance, in the CM100
with hydroxyl ions and promotes the chloride ion ingress, resulting
and CM70F30 samples, the maximum chloride binding capacity is
in increase of total chloride content. Nevertheless, with increasing
observed with w/b = 0.5. However, the CM50S50 samples with w/
chloride penetration depths, the total chloride content of samples
b = 0.45 show the highest chloride binding. Accordingly, it should
exposed to NaCl + Na2SO4 + MgCl2 solutions is higher than the
be noticed that the bound chloride content is affected by high
NaCl + MgCl2 solutions. Additionally, the chloride ingress in mortar
water/binder ratio. This explained that the increase of water /
specimens exposed to NaCl + Na2SO4 solutions show lower than
cement ratio improves the hydration degree of cement and results
other solution in all. This is explained that tricalcium aluminate
in micro pore size of hydration product coarser, which is beneficial
(C3A) can bind with sulfate ions and results in a part of Fs convert-
for the binding capacity. However, it clearly demonstrates that the
ing to ettringite, reduces the channels of chloride ion penetration.
highest total chloride content of the mortar does not indicate the
Previous study also showed that the chloride penetration in ordi-
most bound chloride content. Overall, the results exhibit that all
nary Portland cement concrete was decreased [32]. It was found
mortar specimens exposed to NaCl + Na2SO4 + MgCl2 solution
that the chloride penetration was decreased when the sulfate ions
show the lowest bound chloride content. M100 and M50BFS50
were presence in chloride solutions, which indicated that the pres-
samples exposed to NaCl + Na2SO4 solutions show the highest frac-
ence of sulfate in chloride solutions retarded the chloride ingress.
tion of bound chloride, while the highest bound chloride content is
observed for the M70FA30 specimens exposed to NaCl solution.
Fig. 7 also shows the effects of sulfate and magnesium ion on
3.2. Apparent chloride diffusion
the chloride binding capacity in mortar. CM100 samples with w/
b = 0.5 and CM50S50 with w/b = 0.45 exposed to NaCl + Na2SO4
Fig. 5 shows the apparent chloride diffusion coefficient of mor-
tars immersed in different exposure solutions. It is observed that
exposure solutions and SCMs have obvious impacts on apparent
chloride diffusion coefficient. For the same w/b ratio (0.5), the
apparent chloride diffusion coefficient in M100 mortar exposed
to NaCl + MgCl2 and NaCl + Na2SO4 + MgCl2 solutions is respec-
tively increased by 15.1% and 42.5%, respectively. However, the
apparent chloride diffusion coefficient of mortar samples is
declined by 7.5% when exposed to NaCl + Na2SO4 solutions. This
is explained that the co-existence of chloride and sulfate ion
refines the pore structure and mitigates the chloride penetration
in mortar and thus results in a reduction on the apparent chloride
diffusion coefficient. Furthermore, for CM70F30 samples, the
apparent chloride diffusion coefficient is increased with the incor-
porating of FA due to its slow pozzolanic reactivity [45]. Although
the CM50S50 samples show the highest apparent chloride diffu-
sion coefficient when exposed to NaCl + Na2SO4 solutions, the
incorporation of BFS significantly decreases the apparent chloride
diffusion coefficient in mortar. In contrast to FA, the addition of
BFS is more effective to reduce the apparent chloride diffusion Fig. 6. Chloride binding capacity of mortar samples exposed to different solutions.

Table 5
Correlation between the free chloride content and total chloride content of mortar samples exposed to different solutions.

No. NaCl NaCl + MgCl2 NaCl + Na2SO4 NaCl + Na2SO4 + MgCl2

a R 2
a R 2
a R 2
a R2
CM100 (w/b = 0.4) 1.201 0.979 1.101 0.989 1.156 0.973 1.218 0.993
CM50S50 (w/b = 0.4) 1.295 0.995 1.075 0.998 1.181 0.999 1.095 0.958
CM70F30 (w/b = 0.4) 1.056 0.962 1.081 0.987 1.087 0.961 1.092 0.989
CM100 (w/b = 0.45) 1.157 0.977 1.188 0.998 1.515 0.98 1.057 0.962
CM50S50 (w/b = 0.45) 1.441 0.997 1.089 0.987 1.17 0.965 1.427 0.972
CM70F30 (w/b = 0.45) 1.242 0.959 1.132 0.999 1.084 0.982 1.169 0.996
CM100 (w/b = 0.5) 1.382 0.997 1.138 0.982 1.571 0.989 1.024 0.991
CM50S50 (w/b = 0.5) 1.309 0.993 1.096 0.994 1.169 0.991 1.334 0.986
CM70F30 (w/b = 0.5) 1.461 0.915 1.081 0.975 1.015 0.998 1.008 0.98
 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275
Fig. 7. XRD spectra in the range 5–20° of the mortars at different depths from the surface layer to the inner layer.
solutions show highest binding capacity, while the CM70F30 sam-
ples immersed in NaCl solution have the maximum binding capac-
ity. Overall, mortar specimens exposed to NaCl + Na2SO4 + MgCl2
solutions show the lowest chloride binding. The results demon-
strate that the SO24 in chloride solution enhances the binding
capacity. When the sulfate ion existing in chloride solutions, the
simultaneously diffusion of chloride and sulfate ion into the inte-
rior of matrix reduces the physical absorption accordingly. The
presence of sulfate ion increases the chemical physical absorption
and thus enhances the chloride binding capacity. However, the
Mg2+ and combined Mg2 + and SO2 4 in chloride solution decline
the chloride binding capacity. The reason can be explained that
the magnesium ion in a chloride environment can react with
hydroxyl ions and decrease pH in the pore solution, which has neg-
ative impacts on the release of chemically bound chloride and thus
results in reduction of chloride binding [34]. On the other hand, the
concentration of magnesium ion is also an important factor, indi-
cating that the magnesium ion increased the chloride binding in
high concentration of MgCl2 solution. However, the magnesium
ion content in simulated solutions is limited, which cannot
increase the chloride ion binding.
271
Additionally, chloride binding capacity of mortar exposed to
NaCl + Na2SO4 solutions is reduced prominently with the incorpo-
rating of BFS and FA. This phenomenon can be attributed to the
higher alumina-rich of BFS and FA, namely the higher Al2O3 to
SO3 ratio, which results in formation of more AFm phases and
hence increase the potential for forming Fs [36]. Thus, the presence
of sulfate in chloride solution enhances the chloride binding capac-
ity and reduces the apparent chloride diffusion coefficient in the
high quantity of aluminate in cementitious materials.
3.4. Corrosion products
3.4.1. X-ray diffraction analysis
Samples with w/b = 0.5 is used to explore the corrosion prod-
ucts of exposed mortar under different solution. In order to avoid
the impacts of quartz diffraction peak, the XRD pattern of 5–20°
is selected. The corrosion products of exposed mortar at different
depths are analyzed and the results are illustrated in Fig. 7. The
patterns show that a diffraction peak of Fs for mortar samples
exposed to different solutions appears at the outmost layer as
shown in Fig. 8(a). However, with the increasing of penetration
272 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275
Fig. 8. DTG curves of (a) CM100; (b) CM50S50 and (c) CM70F30 samples mortar at
different depths from the exposed surface (w/b = 0.5).
depths, it is observed that the diffraction peak of Fs shifts to the left
when the mortar specimens are exposed to NaCl + MgCl2 solutions
from Fig. 7(b)–(d). This is ascribed to the low bound chloride con-
centration in NaCl + MgCl2 and NaCl + Na2SO4 + MgCl2 solutions.
The evolution of AFm phases is strongly depended on the concen-
tration of chloride ions and tended to the formation of solid solu-
tion between Fs and OH-AFm at low concentrations (0.05 and
0.15 M chloride) [21]. On the other hand, considering the CO2 3 in
the cementitious system, OH-AFm phase is converted to CO3-
AFm and formed an intermediate phase hemicarboaluminate
(Hc). Additionally, a study argued that the solid solution between
Fs and Hc was probably existed [22].
Fig. 9. Fs (a) and CH (b) content of mortar exposed to exposure solution at different
depths (w/b = 0.5).
The XRD patterns of mortars exposed to the NaCl + Na2SO4 solu-
tions reveal that there is no shift in diffraction peak of Fs. This is
attributed to instability of OH-AFm when the sulfate and chloride
coexisted in a system. Moreover, the Hc could convert to Fs at a
high chloride concentration. Thus, for the samples exposed to
NaCl + Na2SO4 solutions, a reflection of 11.2° represents the forma-
tion of Fs from XRD patterns. Besides, it can be observed that the
addition of BFS and FA is contributed to produce more Fs at the
outmost layer due to the secondary hydration reactions induced
by BFS and FA (Fig. 8a).
3.4.2. Thermogravimetric analysis
The DTG curves of mortars exposed to simulated solutions at
different depths are illustrated in Fig. 8. There are three major
weight losses for the samples which do not contain chloride. The
peak ranged from 60 to 130 °C is principally ascribed to the dehy-
dration of C-S-H gel and AFt or AFm phases. Portlandite (410–
480 °C) and calcite (650–720 °C) are shown in the dehydration
from the DTG curves. Close to the exposed surface (0–5 mm), it
is observed that an additional weight loss (230–410 °C) appear
when the samples exposed to NaCl, NaCl + MgCl2 and NaCl + Na2-
SO4 solutions. This is related to the dehydration of Fs [16,22,46].
However, weight loss (230–410 °C) of mortar specimens exposed
to NaCl + MgCl2 and NaCl + Na2SO4 + MgCl2 solutions seemly dis-
appear at a depth from exposed surface (15–20 mm). It indicates
that, with increasing chloride penetration depths (15–20 mm), Fs
is probably not existed in chloride and magnesium environment,
which is confirmed by XRD patterns in Fig. 8. However, DTG curves
 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275
Fig. 10. Incremental intrusion of (a) CM100; (b) CM50S50 and (c) CM70F30
samples exposed to exposure solution.
of samples exposed to NaCl + Na2SO4 solution indicate that Fs can
be formed at deeper penetration depths.
Fig. 9 shows the obtained results of Fs and CH content in the
mortar specimens exposed to different solutions, which are calcu-
lated by the TG-DSC curves. Obviously, Fs content in different bin-
der mortar at outmost layer (0–5 mm) is higher than the depths of
15–20 mm except for the CM100 samples as shown in Fig. 9a. Close
to the outmost layer, higher amounts of Fs are observed for the
CM50S50 mortar exposed to the NaCl solution than the CM100
273
Fig. 11. Cumulative intrusion of CM100; (b) CM50S50 and (c) CM70F30 mortar
samples exposed to exposure solution.
samples due to alumina-rich phase of SCMs [16]. However, for
the CM100 exposed to NaCl solution, this trend is opposite. It can
be explained that the decrease of calcium ion induced by carbonat-
ing and dissolving restrain the formation of Fs at the outmost layer
[47,48]. Fs content in CM100 sample exposed to NaCl + MgCl2 and
NaCl + Na2SO4 + MgCl2 solutions is higher than the NaCl solution at
the outmost layer, while the difference in the inner layer is slight.
The results indicate that the existing of Mg2+ and Mg2+ + SO2
4 in a
chloride environment promote the formation of Fs at the outmost
layer, which decreases the chloride ingress channel and results in
274 S. Cheng et al. / Construction and Building Materials 204 (2019) 265–275
less formation of Fs to the inner layer. Overall, the amounts of Fs in
the outmost layer are increased when the BFS is incorporating in
mortar. Additionally, it clear that the CH content of outmost layer
is decreased obviously due to large amount of CH leaching and car-
bonating in Fig. 9b. Mortar samples exposed to NaCl + MgCl2 solu-
tions show lower CH content than other solutions. The results can
be attributed to the magnesium ion from NaCl + MgCl2 and NaCl
+ Na2SO4 + MgCl2 solutions will react with hydroxyl ions and form
the precipitation of brucite, resulting in a reduction of CH content.
Moreover, less contents of CH are observed in the BFS and FA mor-
tars than the control mortars. The decrease of CH content is most
likely the consequence of a further pozzolanic reaction.
3.5. Pore structure
The main pore diameter vs. incremental intrusion and cumula-
tive intrusion of mercury in exposed samples are shown in Figs. 10
and 11, respectively. It can be observed that the most probable
pore diameter of exposed mortar samples (w/b = 0.5) is ranged
from 10 to 50 nm, which is usually considered as less harmful pore
(20–50 nm) [49]. For the CM100 samples, the results demonstrate
that the mortar immersed in NaCl + Na2SO4 solution show a lower
less harmful pore size and volume than that exposed to NaCl solu-
tion. While the presence of magnesium ion in NaCl solution seem
to increasing the harmful pore size. This result is consistent with
the chloride transportation results. It is explained that the presence
of sulfate ion increases the chemical physical absorption of chlo-
ride ion and promotes the formation of Fs, which result in a reduc-
tion of pore size and thus decline the channels of chloride ion
penetration. Although the magnesium ion in a chloride environ-
ment can react with hydroxyl and decrease the pH of pore solution,
the pore structure of samples is not changed obvious when
exposed to NaCl + MgCl2 and NaCl + Na2SO4 + MgCl2 solutions.
Moreover, the incorporating of BFS significantly reduces harmful
pore size. This result is also confirmed by the chloride transporta-
tion results, which further show that the pozzolanic reaction of BFS
can optimize the pore structure and improve the resistance to
chloride ingress [50].
4. Conclusions
The present study is to investigate the effects of sulfate and
magnesium ion on the chloride transport and binding capacity of
Portland cement mortar exposed to simulated seawater. Based on
the results and analysis, the following conclusions can be drawn:
(1) When the hydrated mortar exposed to different simulated
solution after 60 day of exposure, the chloride ion content
of mortar immersed in NaCl + MgCl2 solutions is highest at
the outmost layer (0–5 mm). With increasing chloride pene-
tration depths, the mortar exposed to NaCl + Na2SO4 + MgCl2
solutions shows higher chloride content than other exposure
solutions. Overall, the presence of single magnesium ion and
combined of sulfate and magnesium ion in a chloride envi-
ronment accelerates the chloride ingress, while the sulfate
ion restrains the chloride transportation.
(2) Due to the increasing of chemical physical absorption by sul-
fate ion, the NaCl + Na2SO4 solutions decrease the apparent
chloride diffusion coefficient and enhance the chloride bind-
ing capacity with a chloride concentration of 0.56 mol/L.
However, the magnesium ion and combined of sulfate and
magnesium ion in a chloride environment reduces the chlo-
ride binding capacity and increases the chloride diffusion
coefficient of exposed mortar.
(3) The corrosion products of mortar exposed to different solu-
tions depended strongly on the environment of chloride
ions. The sulfate ion in presence of chlorides promotes the
formation of Fs and decreases less harmful pore size, while
the magnesium ion in NaCl + MgCl2 and NaCl + Na2SO4 + -
MgCl2 solutions induces the formation of Hc phases except
for at the outmost layer.
(4) The partial replacements of cement with 50 wt% BFS signif-
icantly decrease the chloride ion diffusion coefficient and
content in mortar regardless of the type of exposure solu-
tions. Additionally, the incorporating of BFS results in a sig-
nificant reduction of the chloride binding capacity and pore
structure due to its higher fineness and secondary hydration
reaction. Nevertheless, the addition of 30 wt% FA seems have
no obvious influence on the chloride ion profiles and binding
capacity.
Acknowledgements
This study was financially supported by the National Natural
Science Foundation Project of China (No. 51679179), National
Key Research and Development Program of China (No.
2017YFB0310905), YangFan Innovative & Entrepreneurial Research
Team Project (No. 201312C12) and the Fundamental Research
Funds for the Central Universities (WUT: 2017II51GX).
Conflict of interest
None.
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