Construction and Building Materials 154 (2017) 849–856

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Construction and Building Materials

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Deterioration mechanism of plain and blended cement mortars partially

exposed to sulfate attack
Fei Chen, Jianming Gao ⇑, Bing Qi, Daman Shen
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China
Jiangsu Key Laboratory of Construction Materials, Nanjing 211189, China

h i g h l i g h t s

Durability of cement mortars partially exposed to sulfate attack was investigated.

The upper part mainly suffered physical attack, while the low part suffered chemical attack.
2

The water-soluble SO4 contents of cement mortars were measured.

SEM, MIP, XRD and X-CT were used to investigate the microstructure changing.

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

Article history: The degradation of cement-based materials partially exposed to sulfate solution are dramatically serious
Received 28 April 2017 than under ordinary full immersion. To research the damage regime of cement-based materials partially
Received in revised form 2 August 2017 exposed to sulfate attack, the resistance of drying (upper) portion and immersed (lower) portion of both
Accepted 4 August 2017
the plain cement mortars as well as fly ash (FA) and grounded blast furnace slag (GBFS) modified cement
mortars partially immersed in 10% Na2SO4 solution was investigated in this paper. The mass change, rel-
ative dynamic modulus of elasticity, compressive/flexural strength and water-soluble SO2 4 contents were
Keywords:
monitored to show the damage progress. SEM/EDS, XRD, MIP and X-CT were used to investigate the
Deterioration regime
Partially sulfate exposed
microstructure changing.
Fly ash The research results indicated that the deterioration of cement mortars partially immersed in sulfate
Grounded blast furnace slag solution is not only caused by chemical sulfate attack, but also by physical sulfate attack. The upper part
Drying portion of specimens mainly suffer physical sulfate attack, as well as chemical sulfate attack, while the lower part
Immersed portion only suffer chemical sulfate attack. Furthermore, fly ash (FA) have better effect than grounded blast fur-
nace slag (GBFS) on improving the resistance of cement mortars to partially immersed in sulfate solution.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction sulfate ions penetrate into cement-based materials, directly react

Concrete structures in South China Sea region and salt lakes of
west China deteriorated significantly, so it is very important to
indicate the degradation mechanism of cement-based materials
partially immersed in salt solution. In the past years, many
research works had been reported on cement-based materials par-
tially exposed to sulfate solutions [1–6], but are still not reach an
agreement on the deterioration regimes.
Sulfate attack can be categorized as chemical attack and physi-
cal attack, due to its different degradation regimes. Chemical sul-
fate attack is considered a complex physicochemical process. The
⇑ Corresponding author at: School of Materials Science and Engineering, South-
east University, Nanjing, 211189, China
E-mail address: jmgao@seu.edu.cn (J. Gao).
with the cement hydration products-calcium hydroxide (CH) and
form harmful products (such as ettringite and gypsum) [7–9],
resulting in softening, expansion, cracking, spalling and disintegra-
tion of cement-based materials. The damage caused by the crystal-
lization of sulfates in the pores near the drying surface of cement-
based materials without chemical reactions was referred to as
‘‘physical salt attack” by the American Concrete Institute (ACI)
Committee 2011 (Durability of Concrete) [6]. The physical sulfate
attack also calls sulfate salt crystallization or sulfate salt weather-
ing, resulting in progressive surface scaling and flaking of cement-
based materials. For instance, the conversion of anhydrous sodium
sulfate (thenardite, Na2SO4) to the hydrous (mirabilite, Na2SO4-
10H2O) form is associated with 314% volumetric expansion. In
the field of concrete durability, the issues of physical sulfate attack
and chemical sulfate attack cannot be distinguished clearly. Such

http://dx.doi.org/10.1016/j.conbuildmat.2017.08.017
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
850 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856

as Nehdi [10] investigated plain and blended concrete partially
immersed in 5% Na2SO4 solution and exposed to cyclic temperature
and RH consisting of one week at temperature = 20 °C and
RH = 82% followed by one week at temperature = 40 °C and
RH = 31% and indicated that the degradation of the upper part of
concrete was caused by the physical sulfate attack, resulting from
tions of mortars are summarized in Table 2. In addition, MO means mortars with
Portland cement, MSO represents 50% replacement of Portland cement with GBFS
and MFO means 30% replacement of Portland cement with FA.
The mortars specimens were mixed in a mechanical mixer and cast in cuboid
molds of 40  40  160 mm. Mortar specimens were demould after placed in lab
for 24 h, then cured for 60 days at a temperature of 20 ± 2 °C and 95% of relative
humidity.

the transformation of the formed mirabilite to thenardite. By con-

trast, Liu [11] researched the cement and cement + fly ash (25%
dosage) paste partially immersed in different sulfate solutions
and results showed that chemical sulfate attack occurring in the
high concentration sulfate pore solutions of upper part of concrete
in contact with air was likely the cause of the worse deterioration
of the upper part. So the deterioration mechanism of concrete par-
tially exposed to sulfate should be determined.
There are several factors affecting sulfate exposure, such as the
water-to-cement ratio, mineral admixtures (fly ash, grounded blast
furnace slag, silica fume), surface treatments and the environmen-
tal temperature and humility. However, contradictory conclusions
about these factor are still exist. Mehta [12] pointed out the min-
eral additions could increase the deterioration of concrete partially
exposed to sulfate attack due to pore size refinement by mineral
additions promoted the capillary rise of the solution in the con-
crete, giving by the following equation [13,14]:
2cLV cos h
h¼
rg q
2.2. Partially sulfate exposure
Following standard curing, mortar specimens were placed in the laboratory for
24 h to remove excess water from the surface of specimens and keep the surfaces of
the mortars sufficiently dry to provide a uniform basis of comparison. Then their
initial data were detected before sulfate exposure, such as compressive/flexural
strength, mass, dynamic modulus of elasticity (Erd) and also some samples were
extracted from initial mortars for mercury intrusion technique (MIP) as well X-
ray diffraction (XRD) researches. Following that mortars were partially immersed
in plastic containers with 10% sodium sulfate solution up to 60 mm (nearly one-
third of the total height of specimens). In order to minimize the evaporation of sul-
fate solution, each lid of plastic containers was cut out six 40  40 mm openings,
which were equal to the size of mortars, as shows in Fig. 1. The drying portion
was exposed to a room condition with 35 ± 1 °C and 50 ± 5% relative humidity,
which was provided by controlled environmental chambers. The high concentration
of sulfate solution, relative high temperature and low humidity were selected to
accelerate the sulfate attack. Moreover, this temperature and humidity were in
accord with the South China Sea region. In order to keep the solution level up to
60 mm height during this experiment, sulfate solution was frequently replenished
in plastic container and also replaced every month to maintain the solution concen-
tration and PH value.
ð1Þ
2.3. Testing scheme

where h (m) is the height of capillary rise, cLV (N m1) is the liquid/
air inter-facial energy, h is the contact angle, r (m) is the pore radius,
g (kg/m3) is the gravitational acceleration, and q is the density of
solution. On the contrary, Bassuoni [15] showed that fly ash can
improve the resistance of concrete to physical sulfate attack, ascrib-
ing to the pozzolanic effect of fly ash on improving the pore struc-
tures and discounting the continuity of capillary pores.
There are conflicting data as well the contradictory theory
regarding the degradation progress of cement-based materials par-
tially exposed to sulfate attack. Thus, in this paper, fly ash and
grand graduate blast slag modified cement mortars partially
immersed in 10% Na2SO4 solution were investigated to verify the
effect of mineral mixtures on the sulfate exposure. Moreover the
drying and immersed portions of specimens were compared to
determine the degradation mechanism of cement mortars partially
exposed to sulfate solution.
2. Experimental program
During the partially exposure, the mortar specimens were monitored (mass, Erd)
every month. After exposure, salt efflorescence and debris were carefully removed
from the surface of mortar specimens by a nylon brush. Then the specimens were
placed in laboratory with room condition for 6 h to remove the excess water from
the surface of specimens. Subsequently, the mass and Erd were determined. The
mass of the specimens before (M o ) and after (M n ) partially immersed in sulfate
solution were measured on an electronic scale (capacity of 5 kg and an accuracy
of 0.01 g) . Consequently, the mass change (W1) was calculated as follows:
Mn  Mo
W1 ¼  100% ð2Þ
Mo
The relative dynamic modulus of elasticity (Erd) of the specimen under partially
exposure was measured by a nonmetal ultrasonic analyzer (NM-4A, transducer fre-
quency is 50 kHz) every month.
The flexural and compressive strength of specimens were also an important
indicator of mortars degradation. The MO specimens fractured after partially expo-
sure for 6 months, so the flexural and compressive strength of all mortar specimens
were detected after erosion for 6 months. Moreover, the upper part and immersed
part of specimens were under different deterioration regimes, so both the upper
and immersed portions of specimens were determined after 6 months exposure.
The strength of mortars before (So ) and after (Sn ) partially immersed in sulfate solu-
tion were measured on universal testing machine. Consequently, the strength
change (DS) was calculated as follows:

Sn  So
2.1. Materials and methods DS ¼ ð3Þ
So
In this study P I 52.5 Portland cement meeting the requirements of GB175-2007 To identify the penetration of sulfate ions in mortars, the water-soluble SO2 4
standard was used. Class-I fly ash (FA) and grounded blast furnace slag (GBFS) com- contents were determined by ultra-violet and visible spectrophotometer (UVPC).
plying with GB/T 1596-2005 and GB/T 203-2008 were used. The physical properties The powder sample was collected from both the drying and immersed portions of
and chemical compositions of Portland cement, FA, and GBFS are given in Table 1. specimens and passed the 0.15 mm sieve. 2 g powder were taken by an electronic
River sand (<5 mm) with fineness modulus of 2.6 was used. The mixture propor- scale (capacity of 200 g, with a precision of 0.0001 g) after the powder was dried
in an oven at a temperature of 60 °C to achieve constant weight. Following that
the 2 g powder dissolved in 50 ml distilled water and stored for 24 h. Then the
Table 1 whole solution were filtered through slow filter paper and 25 ml of them were
Physical properties and chemical compositions of cement, FA and GBFS. put into colorimetric cylinder (capacity of 50 ml). The extraction solution was
titrated by diluted hydrochloric acid (2.5 mol/l), and added 10 ml BaCl2-PVA mix-
CaO 64.47 5.75 36.35 ture as dispersant, then diluted with distilled water to 50 ml, followed by oscillation
SiO2 20.87 51.07 33.48 2–3 times and standing for 5 min. Then solution was extracted into cuvette and
Al2O3 4.87 30.86 12.21 compared with the blank solution. The wavelength used was 440 nm [16].
Fe2O3 3.59 5.26 1.40
MgO 2.13 2.72 10.60
SO3 2.52 1.48 0.66 3. Results and discussion
K2O 0.65 1.13 0.56
Na2O 0.11 0.79 1.27 3.1. Visual inspection
Physical properties
Specific gravity/(g/cm3) 3.11 2.35 2.82 Visual appearance of MO, MFO, MSO specimens partially
Blaine fineness/(cm2/g) 3689 4000 4600
exposed to 10% Na2SO4 solution are shown in Fig. 2. As Fig. 2(a)
 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856 851

Table 2
Mixture proportion of mortars.

Mix Cement/(kg/m3) FA/(kg/m3) GBFS/(kg/m3) Fine aggregate/(kg/m3) Water/(kg/m3) w/b/(%)

MO 442 – – 1770 288 0.65
MFO 310 133 – 1770 288 0.65
MSO 221 – 221 1770 288 0.65

Fig. 1. Schematic diagram showing the partially exposed mortar specimens.

shows, enormous amount of salt efflorescence in the evaporative
zone of the MO/MFO/MSO specimens after partially immersed in
10% Na2SO4 solution for six months and the thenardite crystal
grow vertically against the surface of specimens. This is result from
that the SO2
4 ions penetrate with water from the immersed por-
tion (lower part) to the drying portion (upper part) by capillary
absorption. While the water vapour evaporate from the surface
of drying portion when specimens under a relative humidity less
than 100% environment, leading to salt deposition on the surface
of specimens and form salt efflorescence. After the salt crystals
are wiped off, the salt efflorescence only develop above the solu-
tion level in all specimens and no significant damage is observed
from the immersed portion of MFO specimen, see in Fig. 2(b). By
contrast, the immersed portion of MSO specimen suffer seriously
surface scaling and flaking, which is typical caused by chemical
attack of sulfate solution, as well some salt efflorescence occur in
the drying portion. Although not obviously salt scaling develop in
the MO specimen, but cracks expand severely in the evaporative
zone and even extend to the immersed and upper portion. It is
clearly from Fig. 2(b) and (c) that, the top part of MO/MFO/MSO
specimens are almost intact after erosion.
3.2. Mass change
Fig. 3 shows the mass change of MO/MFO/MSO specimens par-
tially exposed to 10% Na2SO4 solution. The MO and MSO specimens
are fractured after exposure for 6 months and 7 months, respec-
tively, but the MFO specimen has not broken until partially

Fig. 2. Visual appearance of MO, MFO, MSO specimens (from left to right) partially exposed to 10% Na2SO4 solution: (a) specimens during experiment; (b) specimens after the
salt crystals are removed.
852 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856

12 MO
MO 1.3 MFO
MFO
8 1.2 MSO
MSO
Mass Change (%)

1.1
4
1.0
0 0.9

Fracture

E rd
0.8
-4
0.7

-8 0.6

0.5
-12
0 1 2 3 4 5 6 7 8 9 0.4
0 1 2 3 4 5 6 7 8 9
Time (months)
Time(months)
Fig. 3. Mass change of MO/MFO/MSO specimens partially exposed to 10% Na2SO4
Fig. 4. Erd variation of MO/MFO/MSO specimens partially exposed to 10% Na2SO4
solution.
solution.

immersed for 9 months, which indicate that fly ash and grounded
blast furnace slag can improve the resistance of mortars to partially
immerse in sodium sulfate. Moreover, comparing with GBFS, FA
has better effect on the resistance to sulfate attack. As Fig. 3 shows,
the mass of MSO specimen decrease significantly after exposure for
7 months, which is mainly due to the surface scaling and flaking
(see Fig. 2(b)) and caused by chemical attack of sodium sulfate.
By comparison, the weight of MO specimen still increase slightly
when it is fractured, this is on account of no obvious surface scaling
occur in specimen (Fig. 2(b)) on one hand and large amount of
chemical erosion products-ettringite and gypsum and physical ero-
sion product-thenardite of sulfate attack deposit in MO specimen
on the other hand. The little mass change of MFO specimen also
shows a better resistance of FA to sulfate exposure.
3.3. Erd change
The Erd variation of MO/MFO/MSO specimens partially exposed
to 10% Na2SO4 solution are shown in Fig. 4. Comparing with the
slightly weight change of MO specimen, the Erd of MO decrease sig-
nificantly and reach 0.5 after partially exposure for 6 months, this
is due to the large amount of cracks in specimen. On the contrary,
the Erd of MSO specimen decrease slightly after errored for
5 months, although its mass reduce obviously. It is found that
weight loss and Erd cannot reveal the degradation of mortar spec-
imens partially immersed in sulfate solution individually, because
although salt scaling will reduce the mass of specimens, but sulfate
can also penetrate into specimens by capillary absorption and react
with calcium hydroxide, form ettringite and gypsum, which lead to
increment of the weight. The deterioration degree of specimens
should be indicated by together with weight loss and Erd. Because
of the severely surface flaking in the immersed portion (Fig. 2(b))
the MFO specimen increase, which are in accordance with the Erd
results (Fig. 4). It is result from erosion products, such as ettringite
and gypsum, fill the inner pores of mortars and compact speci-
mens, which promote the flexural and compressive strength of
MFO mortars. But with the progressive penetration of sulfate ions,
more ettringite and gypsum expand in mortar and generate cracks
and surface scaling, leading to the reduction of strength, like MO
and MSO specimens. After partially exposure for 6 months, the
MO specimen is fractured, so the flexural loading drop by 100 per-
cent. Although the MSO specimens suffer serious surface scaling
and flaking, the flexural loading loss are still lower than MO spec-
imens. The compressive strength loss of the drying portion of MO
and MSO is lower than that of immersed portion, this is because
that the sulfate ion deposit in the evaporative zone of specimens,
so the top parts of specimen are under less sulfate attack, while
leading to the less increase for MFO specimens at the same time.
3.5. SO2
4 diffusion
The standard curve of sodium sulfate standard solution (1 ml
solution contained 1 mg SO24 ) determined by UVPC is shown in
Fig. 6. The nonlinear model based on quadratic polynomial equa-
tion is as follows:
2
f ðabsÞ ¼ 2:58154abs þ 2:08744abs þ 0:22124 R2
¼ 0:99106 ð4Þ
Flexural strength
1.0
Compressive strength of drying portion
Compressive strength of immersed portion
0.5
Strength Change

of MSO specimen, so the progressive Erd of MSO cannot been mea-

sured after 5 months. The Erd of MFO specimen fluctuate and
0.0
increase slightly over time, it is on account of ettringite and gyp-
sum which fill the interior pores and compact specimen.

-0.5
3.4. Flexural and compressive strength

Flexural strength and compressive strength of drying/immersed

portions for MO/MFO/MSO specimens after 6 months partially -1.0
MO MFO MSO
exposed to 10% Na2SO4 solution are shown in Fig. 5. It is obviously
that no matter flexural and compressive strength of MO and MSO Fig. 5. Flexural strength and compressive strength of drying/immersed portions of
specimens drop down after erosion for 6 months, while that of MO/MFO/MSO specimens after 6 months partially exposed to 10% Na2SO4 solution.
 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856 853

12 2.5
Sodium sulfate standard solution Drying portion
10 Polynomial fit Immersed portion

Water-soluble SO42- content

2.0

8
SO42- (mg)

1.5

6
1.0
4

0.5
2

0.0
0
MO MFO MSO
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Fig. 7. Water-soluble SO2
4 content of drying/immersed portions of MO/MFO/MSO
Absorbance [%] specimens after 6 months partially exposed to 10% Na2SO4 solution.

Fig. 6. Standard curve of sodium sulfate standard solution.

15
Water-soluble SO2 4 content of drying/immersed portions of MO before corrosion
MO/MFO/MSO specimens after 6 months partially immersed in
MFO before corrosion
10% Na2SO4 solution are shows in Fig. 7. The samples which are
used to determine the sulfate concentration of the upper part are
MSO before corrosion
10
collected in the efflorescence zone [17] of specimens. It is obvi-
Porosity (%)
ously that the water-soluble sulfate concentration of drying por-
tion are higher than in the immersed portion for no matter the
plain mortar or FA and GBFS modified mortars. This is result from
the sulfate ions transport from the lower part towards the upper 5
part of mortars with water by the capillary absorption, while the
water would also evaporate from the drying portion of specimens
[18], leading to a dry-wet interface in specimens, where the rate of
salt solution entering the mortars by capillary sorption match the 0 (a)
rate of water leaving the drying face of the mortars by water
vapour diffusion [11]. So the sulfate salt accumulate in the efflores- 1 10 100 1000 10000 100000
cence zone, which can not only caused physical sulfate attack, but
Pore diameter (nm)
also chemical sulfate attack, resulting in the several deterioration
in the drying portion, see Fig. 2. It is also from the Fig. 7 that, the 20
water-soluble SO2 4 concentration of MO specimen is much higher
than in MFO and MSO specimens, which also due to the less degra- Drying portion of CO
dation of MFO and MSO specimens, see Fig. 2. CO before corrosion
15
Immersed portion of CO
3.6. Alteration of microstructures
Porosity (%)

10
3.6.1. MIP
Fig. 8 shows the pore size distributions for MO/MFO/MSO
before erosion or erosion for 6 months. As the Fig. 8(a) shows,
although the total porosity of MFO specimen before erosion is 5
13.5%, which is higher than the total porosity of MO and MSO
and are 11.8% and 11.5%, respectively. But the main pores of
MFO specimen are less than 100 nm, which are harmless pore to (b)
0
sulfate attack. On the contrary, MO specimen have the maximum
harmful pores, which are larger than 200 nm, followed by MSO 1 10 100 1000 10000 100000
and MFO specimens and which are 6.3%, 5.5% and 4.8%, respec-
Pore diameter (nm)
tively. This results indicate that mortars comprising FA and GBFS
have finer pore structures compared with the plain mortars, which Fig. 8. Pore size distributions for MO/MFO/MSO specimens (a) MO/MFO/MSO
is due to the micro-aggregate and pozzolanic effect of mineral before erosion; (b) immersed and drying portion of MO after partially exposed to
admixtures, leading to the less penetration of sulfate ions (Fig. 7) 10% Na2SO4 solution.

and damage of MFO and MSO specimens (Figs. 4 and 5). As

expected, the total porosity of drying and immersed portion of
MO specimen after partially exposure for 6 months are higher than
MO specimen before erosion. This is on account of the expansive
erosion products expanding in mortars and forming large amount
of cracks in MO specimens, as shows in Fig. 2(b). Moreover, owning
to large amount of micro-cracks generate in the evaporation zone
of specimens, the total porosity of drying portion is higher than
that of immersed portion.
3.6.2. XRD
XRD patterns of MO/MFO/MSO specimens partially exposed to
10% Na2SO4 solution are shown in Fig. 9. The sample of drying part
854 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856

for MO specimen is picked from the surface of the fracture in the E-Ettringite
efflorescence zone. It is clearly that the strongest peak of drying G Q P-Portlandite
(a) Th Q-Quartz
portion for MO specimen after partially exposure for 6 months is
thenardite, suggesting significant salt efflorescence in the evapora- C-Calcite
Q G-Gypsum
tive zone of specimen, whilst is the weakest peak for the immersed E P C P
G T-Thenardite
portion of MO specimen. There are also chemical reaction products, T G T T Th-Thaumasite
E
ettringite and gypsum in the drying portion, so specimen in the
Immersed portion
drying portion suffer combined physical and chemical sulfate T
attack under partially exposed to sulfate solution, furthermore, T
massive thenardite substantiate that salt crystallization is the driv-
Drying portion
ing mechanism for cracks in the evaporation zone of specimen,
which match the previous studies of Haynes [19]. On the contrary,
the main peak of immersed portion of MO specimen after erosion
Before erosion
for 6 months is gypsum and somewhat ettringite, owning to the
chemical attack of sulfate. The high SO2 4 content by capillary rise
5 10 15 20 25 30 35 40
and form a low PH environment by reacting with CH are two main
2θ(°)
reasons for the low ettringite in the specimen. These results indi-
cate that the main sulfate attack in the immersed portion for spec- Q E-Ettringite
imen suffer partially exposure is chemical attack. P-Portlandite
Comparing with the upper part of MO specimen, the peak of Q-Quartz
thenardite in the upper part of MFO and MSO samples is much (b) T C-Calcite
T T
lower, furthermore the peak of gypsum in the immersed part of P G-Gypsum
ETGC T-Thenardite
MO sample is also higher than that in the MFO and MSO samples G Q T
at the same time. The increased physical and chemical resistance G Q
of fly ash mixtures can be attribute to the pozzolanic effect of fly MO
ash on improving the pores structures and reducing the continuity
of capillary pores, as have been discussed in the literatures [12,20].
MSO
Moreover, this pozzolanic effect might be minor before erosion,
while increasing gradually over the partially exposure. By contrast,
although grounded blast furnace slag can refine the pores sizes MFO
better at the beginning (seen in Fig. 8(a)), but due to the low activ-
ity of aluminum in GBFS, accompanying low pozzolanic effect, the 5 10 15 20 25 30 35 40

pores structure of GBFS modified mortars become worse than MFO 2θ(°)
specimen with the penetration of sulfate ions, so show the poor
resistance to sulfate attack, but still better than specimens without E-Ettringite
G Q
mineral mixtures. On the other hand, the much lower peak of CH P-Portlandite
for MFO and MSO specimens than for MO specimen in Fig. 9 Q-Quartz
(b) and (c) is also a strong evidence. (c) Th C-Calcite
G-Gypsum
Q T-Thenardite
E P
GC P Th-Thaumasite
G E
3.6.3. SEM Q
The SEM images and EDS results of the immersed portion and MO
drying portion for MO specimen partially exposed to 10% Na2SO4 T
solution are shown in Fig. 10. It is clearly that the SEM image of MFO
the drying portion of MO sample show abundant micro-cracks in
the cement paste, especially in the ITZ between the cement paste
and aggregate, which is accordance with the visual inspection
MSO
(Fig. 2(b)). Abundant crystals with different morphologies and
sizes are detected there, and the main elements are Na, S and O 5 10 15 20 25 30 35 40

determined by EDS result, so it is thenardite. At the same time, sul- 2θ(°)

fate erosion products-gypsum and ettringite are also incidental
features in most samples extracted from the drying portion, which
indicate that the deterioration of in the drying portion of cement
mortar under sulfate solution is mainly caused by physical attack
as well chemical attack, which is accordance with the XRD results,
show in Fig. 9(a).
On the contrary, the sample taken from the immersed portion
are detected as some irregular sheets and sharp needle-like crys-
tals by SEM images, which are typical sulfate chemical reaction
products-gypsum and ettringite and can be verified in EDS results.
Comparing with little ettringite, gypsum can be found in all of the
SEM images, which is in accord with the XRD results. However,
minor damage manifestations including lack of swelling and crack-
ing indicate that only chemical sulfate attack in the immersed por-
tion is insignificant compared with the combined physical and
chemical attack in the drying portion.
Fig. 9. XRD patterns of MO/MFO/MSO specimens partially exposed to 10% Na2SO4
solution: (a) MO specimen; (b) drying portion; (c) immersed portion.
3.6.4. X-CT
The 3D visualizations and cross-sectional images of MO/MFO/
MSO specimens determined by X-CT of specimen partially exposed
to 10% Na2SO4 solution are shown in Fig. 11. As Fig. 11(a) shows,
abundant micro-cracks extend in the whole subflorescence zone
of MO specimen, moreover a big crack nearly cross the specimen
(Fig. 11(d)), which lead to its fracture in 6 months. Comparatively,
no obvious cracks in the interior of MFO and MSO specimens
except some micro-cracks and scaling on the surface, leading to
less strength and Erd loss (Figs. 4 and 5). The MFO sample is almost
intact after partially exposed to 10% Na2SO4 solution and only
some micro-cracks occur in the surface of immersed portion (seen
 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856 855

Fig. 10. SEM images and EDS results of MO specimen partially exposed to 10% Na2SO4 solution: (a)–(c) drying portion; (d)–(f) immersed portion.

Fig. 11(b, e)), which are typically caused by chemical attack. The
top portion of MSO specimen is also intact after erosion, whilst
severely salt swelling and cracking is observed in the immersed
portion and evaporative zone. It is found fly ash and grounded blast
furnace slag can improve the resistance of cement mortar to phys-
ical and chemical attack.
4. Conclusions
The degradation of cement-based materials partially exposed to
sodium sulfate solution is a critical durability problem in maritime
regions and salt lakes, leading to the surface scaling and even
fracture, which is much more serious than ordinary full immersed
856 F. Chen et al. / Construction and Building Materials 154 (2017) 849–856
Fig. 11. 3D visualizations and cross-sectional images determined by X-CT of
specimen partially exposed to 10% Na2SO4 solution: (a, d) MO; (b, e) MFO; (c, f)
MSO.
concrete structures. According to the results obtained in this study,
the following can be concluded:

The weight loss and relative dynamic modulus of elasticity can-
not reveal the degradation of mortar specimens partially
immersed in sulfate solution individually, the degradation
degree of specimens should be determined by together with
weight loss and relative dynamic modulus of elasticity.

Owing to the reciprocal action between capillary absorption
and evaporation of water vapour for cement mortars partially
immersed in 10% Na2SO4 solution, the sulfate concentration in
the drying portion of plain mortar or fly ash and grounded blast
furnace slag modified mortars are higher than in the immersed
portion.

The immersed portion of cement mortars partially exposed to
10% Na2SO4 solution is mainly suffered chemical sulfate attack.
On the contrary, the upper part of specimens partially
immersed in 10% Na2SO4 solution is not only suffered chemical
sulfate attack, but also under physical sulfate attack, moreover
the physical attack is the driving mechanism.

Comparing with plain cement mortars, fly ash and grounded blast
furnace slag can improve the resistance of cement mortars par-
tially exposed to sulfate solution, resulting from the continuous
pozzolanic effect, which decrease the continuity of capillary
pores.
Acknowledgements
This work was supported by National Natural Science Founda-
tion of China (grant no. 51578141 and 51278096), the Major State
Basic Research Development Program of China (grant no.
2015CB6551002) and Ministry of Science and Technology of China
(grant no. 2016YFE0118200). The authors would like to thank the
Major State Basic Research Development Program of China, the
Natural National Science Foundation and Ministry of Science and
Technology of China for the financial support for this project.
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