Construction and Building Materials 227 (2019) 116678

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Construction and Building Materials

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

Integral hydrophobic concrete without using silane

Zhijun Feng, Fajun Wang ⇑, Ting Xie, Junfei Ou, Mingshan Xue, Wen Li
School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, PR China

h i g h l i g h t s

SAE was used as a hydrophobic admixture for cement mortar.

The MCM exhibits integral hydrophobicity.

The hydrophobic MCM is robust against various mechanical damages.

The capillary water absorption of the MCM decreased significantly.


The MCM shows improved corrosion resistance for steel against Cl .

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

Article history: The high cost of silane and siloxane based water repellent agents limits their large scale applications in
Received 4 June 2019 concrete. In the present work, a low cost waterborne stearic acid emulsion (SAE) was introduced to
Received in revised form 30 July 2019 improve the water repellent properties and corrosion resistance of cement mortar (CM). Compared with
Accepted 7 August 2019
the unmodified cement paste (CP), the introducing of SAE in CP generally reduced the fluidity and setting
time, but increased the standard consistency water consumption of the CP. The CM modified with 1.0 wt%
SAE exhibits integral hydrophobicity, with contact angles larger than 130° on both the as-prepared sur-
Keywords:
face and the fractured surface (inner surface). The hydrophobic surface of the SAE modified CM is robust
Stearic acid emulsion
Cement mortar
against mechanical damages. In addition, compared with the control sample, the water absorption of the
Hydrophobicity modified CM decreased by 86.06%, while the corrosion resistance against chloride ion increased
Water absorption significantly. Moreover, the compressive strength and flexural strength of the SA modified CM decreased
Corrosion resistance compared with the control sample, but the reduction was within 20%.
Mechanical robustness Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Portland cement and concrete materials are widely used in the
fields of roads, bridges, dams and buildings, and so forth [1,2].
Cement based concrete has porous structure and hydrophilicity,
so water permeates easily in the concrete structure. Water sources
in nature are usually impure and contain various ions. Chloride ion,
sulfate ion, hydrogen ion, carbonate ion and magnesium ion in
aqueous solution are corrosive to concrete structure [3–5]. During
the use of concrete materials, it is inevitable to contact with vari-
ous water sources in the environment, such as seawater, river
and lake water, acid rain and melted water containing melted ice
salt, and so forth. The corrosive ions contained in these water
sources enter the concrete interior with the infiltration of water
into the concrete structure, causing erosion to the concrete. In
coastal areas and areas where ice-melting salt is widely used,
⇑ Corresponding author.
E-mail address: jjbxsjz@foxmail.com (F. Wang).
chloride ions cause severe corrosion to steel bars in reinforced con-
crete members, resulting in a significant decrease in mechanical
strength and a sharp decline in service life. Since the penetration
of water is a necessary condition for the erosion of concrete, reduc-
ing the permeability of concrete is an effective method to improve
its erosion resistance and thereby improve its durability [3–5]. At
present, hydrophobic modification of concrete is one of the most
commonly used methods to reduce the permeability of concrete,
which has attracted extensive attention in fundamental research
and practical application [6–9].
There are two main methods for hydrophobic modification of
cement concrete, namely, surface hydrophobic modification
method and integral hydrophobic modification method [2,5–10].
The surface hydrophobic modification method is a surface
treatment of the formed concrete by impregnating or coating.
Xue et al. prepared a waterborne hydrophobic agent using octyltri-
ethoxysilane [11]. Then the mortar and concrete sample surfaces
were impregnated using the homemade hydrophobic agent. The
capillary water absorption of the modified cement mortar was

https://doi.org/10.1016/j.conbuildmat.2019.116678
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678
reduced by 94.6% compared with the unmodified one. Li et al. pre-
pared a nanocomposite coating consisting of nano SiO2 and poly-
methylhydrosiloxane (PHMS) [12]. After modified with the SiO2/
PHMS nanocomposite coating, the water absorption of one-year-
old cement mortar sample is 85.96% lower than that of the control
sample. However, the disadvantage of surface hydrophobic modifi-
cation method is obvious. The hydrophobic layer only exists on the
surface of concrete. When the surface of concrete cracks or wears
in the long-term use, the newly exposed surface of concrete is still
hydrophilic. The impermeability of the concrete decreases rapidly
after the surface hydrophobic layer is destroyed.
The integral hydrophobic modification method uses hydropho-
bic admixture to the fresh concrete during the mixing process
[2,13–19]. The hydrophobic concrete prepared by this method
exhibits integral hydrophobicity. During the use of the integral
hydrophobic concrete material, the newly exposed surface is still
hydrophobic and its impermeability will not be affected even after
the surface is worn and cracks occur. Therefore, compared with
surface hydrophobic modification method, the integral hydropho-
bic modification method has better durability. The hydrophobic
additives used are mainly silane, silicone, hydrophobic powders,
waste rubber powder and the like [13–19]. These hydrophobic
additives have obvious disadvantages in practical use. Zhu et al.
used octyltriethoxysilane based material as an integral hydropho-
bic agent to improve the water repellent property and durability of
the concrete [13]. The results showed that after the modification,
the durability of concrete improved, but the mechanical strength
of concrete reduced. Subbiah et al. prepared a hydrophobic admix-
ture by mixing 1H,1H,1H,2H-perfluorodecyl-triethoxysilane
(PFDTS), nano SiO2 and nano TiO2 in water [5]. The modified
cement mortar exhibits hydrophobicity, low water absorption
and high durability. However, silanes and siloxanes are expensive
and cannot be widely used in concrete. Hydrophobic powders were
also applied as integral additives for concrete to reduce the water
absorption [14,15]. However, these hydrophobic powders were
non-commercial materials, their processing processes were com-
plex. In addition, the hydrophobic powder was difficult to uni-
formly disperse in water. While the introduction of hydrophobic
waste tyre rubber powder drastically reduced the strength of con-
crete [16]. Therefore, it is urgent to develop novel hydrophobic
additives which are cheap and have smaller effect on the mechan-
ical strength of concrete.
Stearic acid is a cheap hydrophobic modifier, which is widely
used in the preparation of superhydrophobic materials
[14,15,17]. However, stearic acid is a solid at room temperature
and insoluble in water. Therefore, it is difficult to uniformly dis-
perse SA in concrete at room temperature [14]. Other methods
have been tried to introduce stearic acid into concrete. For exam-
ples, stearic acid coated powders and stearic acid derivatives (such
as calcium stearate and zinc stearate) are used [14,15,17,20].
Unfortunately, these powders derived from stearic acid are highly
hydrophobic or even superhydrophobic, and they are difficult to
disperse uniformly in water.
Table 1
Mix proportion of SAE modified cement mortar.
Sample (#) SA content (wt%)
1 0% (SAE = 0.00 g, Water = 0.00 g)
2 0.2% (SAE = 3.00 g, Water = 2.10 g)
3 0.4% (SAE = 6.00 g, Water = 4.20 g)
4 0.6% (SAE = 9.00 g, Water = 6.30 g)
5 0.8% (SAE = 12.00 g, Water = 8.40 g)
6 1.0% (SAE = 15.00 g, Water = 10.50 g)
7 1.5% (SAE = 22.50 g, Water = 15.75 g)
8 2.0% (SAE = 30.00 g, Water = 21.00 g)
In this work, waterborne stearic acid emulsion (SAE) was used
as hydrophobic admixture for cement mortar (CM) to improve
the impermeability of CM. The waterborne SAE is a cheap and com-
mercial available product. Because it is an aqueous emulsion, the
SAE can be easily dispersed in CM. To the best of our knowledge,
the use of SAE as a hydrophobic admixture for CM have not been
reported in literature. The purpose of this work is to explore the
effect of SAE on the workability, wettability, water absorption, cor-
rosion resistance and mechanical properties of CM. This work will
provide experimental basis and application reference for the devel-
opment of low-cost, silane-free durable concrete.
2. Materials and methods
2.1. Materials
Stearic acid aqueous emulsion (SAE, stearic acid content is 30 wt%) was pur-
chased from Luoyang xinyu environmental protection technology Co., Ltd. Ordinary
Portland cement (P.O 42.5) was purchased from Huaxin cement co. LTD. Standard
sand was provided by Fujian Tianliao standard sand co. LTD. Deionized water
(DW) was prepared using a deionized water equipment in our lab.
2.2. Preparation of SA modified cement mortar
A batch of SAE modified cement mortar samples were prepared using a JJ-5 pan
mixer according to the mix proportion depicted in Table 1. For each mortar mixture,
40  40  160 mm prisms were cast for flexural strength, compressive strength and
water adsorption test, and 33  38  25 mm cuboids were cast for water contact
angle (CA), surface topographies and surface chemical compositions measurements.
The water to cement ratio and cement to sand ratio is 0.4 and 1/3, respectively. The
specimens were taken out from the molds after 48 h. Then, they were cured under
condition of 25 ± 3 °C and 90% relative humidity. The prism specimens were cured
until the ages of 3, 7, 28 and 90 days for strength measurement. Other specimens
were cured for 28 days and then used for other tests and analyses.
3. Measurement and characterization
3.1. Workability
The fluidity of the cement paste was measured using an NLD-3
cement mortar fluidity tester according to the standard method
(Chinese standard GB/T 2419-2005). When the test bar sank into
the cement paste and is 6 ± 1 mm away from the bottom plate,
the corresponding cement paste is the cement paste of standard
consistency, and the mixing water amount is defined as the water
consumption of the standard consistency of the cement.
The standard consistency water consumption (abbreviated as
SCWC) and the setting time of the cement paste were measured
using a Vicat apparatus as per Chinese standard GB/T 346-2011.
When the test rod sank into the cement paste and is 6 ± 1 mm away
from the bottom plate, the corresponding cement paste is the stan-
dard consistency paste, and the mixing water amount is defined as
the standard consistency water consumption of the cement. For
the setting time measurement, when the initial setting needle sank
to a position of 4 ± 1 mm from the bottom plate, the cement reaches
the initial setting state, and the corresponding time is defined as the
Cement Sand Water Total water
450 g 1350 g 180 g 180 g
450 g 1350 g 177.9 g 180 g
450 g 1350 g 175.8 g 180 g
450 g 1350 g 173.7 g 180 g
450 g 1350 g 171.6 g 180 g
450 g 1350 g 169.5 g 180 g
450 g 1350 g 164.25 g 180 g
450 g 1350 g 159 g 180 g
 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678 3

initial setting time. When the final setting needle sank into the sam-
ple 0.5 mm, the cement reaches the final setting state, and the corre-
sponding time is defined as the final setting time. Each result was
tested three times and then averaged for analysis.

3.2. Surface wettability

Water contact angle (CA) and water sliding angle (SA) on sam-
ple surfaces were measured using an optical contact angle measur-
ing device (DSA30, Krüss, Germany). Deionized water was used as
test liquid. The volume of water droplet is fixed at 8 ml. The CA was
measured at different positions on the sample surface and the
average value of five measurements was taken as the reported
value of CA. For SAs measurements, a water droplet water is care-
fully placed on the sample surface, and the sample is slowly tilted.
When the water droplet begins to roll, the corresponding tilt angle
is defined asthe rolling angle. Similarly, the average of five SA mea-
surements was taken as the reported value for analysis.

3.3. SEM and XPS measurement

The surface micromorphology of the samples was observed by

field emission scanning electron microscope (Quanta 250 SEM,
USA). The surface chemical composition of the sample was ana-
lyzed by X-ray photoelectron spectroscopy (ESCALAB 250Xi, USA).

3.4. Pore structure analysis

The pore structure of cement mortar sample was measured

using a mercury intrusion porosimetry (MIP, Quantachrome, Pore-
master 60, USA).

3.5. Capillary water absorption

The capillary water absorption of the modified cement mortar

and the unmodified cement mortar were measured according to
the standard method [ISO 15148:2002(E)]. The capillary water
absorption test was carried out using cubic samples having a size
of 10 cm  10 cm  10 cm. The four lateral sides of the cube sam-
ple were sealed with an epoxy resin. Before immersion test, the Fig. 1. Image of the experimental cell with the tested sample for polarization curves
measurement: (a) the experimental cell; (b) the tested samples; (c) a schematic
samples were dried to constant weight at 105 °C. The samples were
diagram of steel sheet embedded in cement mortar.
place in a tank containing point supports so that the bottom of the
sample is separated from the bottom of the tank.
was used as the corrosion solution during the test. All samples
The water immersion depth of the sample was 5 mm, and the
were tested after soaking for 1 day in sodium chloride solution.
water absorbed by the sample was measured after different soak-
ing time up to 96 h. The capillary absorption curves of samples
3.7. Mechanical strength measurement
could be obtained by using the following equation [13]:
pffiffi
DW ¼ A t ð1Þ The compressive strength and the flexural strength of the
cement mortar samples were measured following the Chinese
where DW is the capillary water absorption (g/m2), A is the capillary standard (GB/T 17671-1999). Prism samples with a size of
absorption coefficient and t is the immersing time (h). 40 mm  40 mm  160 mm [see Fig. 2(a) and (b)] were used to test
the flexural strength, and the average flexural strength of the three
3.6. Electrochemical measurement samples was used as the reported value. Fractured samples after
flexural strength test [see Fig. 2(c)] were cut into 2 cubes [see
Steel sheet (45#, 20 mm  40 mm  0.2 mm) was partially Fig. 2(d), 40 mm  40 mm  40 mm] and used for compressive
embedded into the fresh cement mortar in the process of cement strength measurement. The average compressive strength of 6
mortar molding. Half of the steel sheet (20 mm  20 mm  samples was taken as the reported value.
0.2 mm) is exposed outside the mortar as working electrodes
[see Fig. 1]. The samples were cured under the method described 4. Results and discussion
above for 28 days. The platinum electrode was used as the counter
electrode, and the silver/silver chloride electrode was used as the 4.1. Workability analysis
reference electrode. A computer-controlled electrochemical work-
station (Reference 3000, Gamry, USA) was used to obtained the Cement paste (CP) samples were prepared and used to investi-
polarization curves of the samples. A 3.5% sodium chloride solution gate the influence of SAE on the the workability of CP and the
4 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678
Fig. 2. (a) and (b) photos of 40  40  160 mm prisms for flexural strength test; (c)
40  40  160 mm prism after flexural strength test; (d) The fractured sample were
cut into cubes (40  40  40 mm) for compressive strength testing.
results were depicted in Fig. 1. One can see that the fluidity [Fig. 3
(a)] of the CP decreases with increasing SA content, which indicates
that the addition of SAE hinders the flow of the CP. As depicted in
Table 1, the total water used in the CM is fixed at 180 g (water to
cement ratio is 0.4), which includes the water in the SAE. There-
fore, with the addition of SAE, the solid content in CP increases,
resulting in increased consistency and reduced fluidity of the CP.
The more the SAE is added, the worse the fluidity of the CP.
Fig. 3(b) shows the SCWC of SAE modified CP samples are also
increases with increasing SA concentration. It can be explained
by the fact that under the premise of constant water consumption,
the total solid content of SA modified CP increases with the addi-
tion of SAE. The more solid content, the greater the consistency
of the CP. In other words, the SAE modified CP requires more water
when the same consistency of the CP is reached. According to Chi-
nese national standards, the initial setting time of Portland cement
should not be shorter than 45 min, and the final setting time of
Portland cement should not be longer than 6.5 h. Fig. 3(c) shows
that both the initial setting time and the final setting time of the
CP decrease slowly with the increase of SA content. However, the
Fig. 3. Influence of SA content on the fluidity, standard consistency water consumption and setting time of SAE modified cement pastes.
setting time of all samples is within the allowable range. The main
components of Portland cement are tricalcium silicate (3CaOSiO2
or C3S) and dicalcium silicate (2CaOSiO2 or C2S). Their hydration
products are hydrated calcium silicate gel (CSH) and calcium
hydroxide (CH). The hydration reaction of C3S and dC2S are shown
in the following Eqs. (2) and (3) [21]:
C 3 S þ H2 O ¼ CSH þ CH ð2Þ
C 2 S þ H2 O ¼ CSH þ CH ð3Þ
The hydration product CH further reacts with SA to produce cal-
cium stearate, as shown in Eq. (4) [22]:
 
CaðOHÞ2 þ CH3 ðCH2 Þ16 COOH ¼ Ca OOC ðCH2 Þ16 CH3 2 þ H2 O ð4Þ
Therefore, the addition of SA not only consumes CH, but also
produces water, both of which promote the hydration of the
cement. Therefore, the setting time of the CP is shortened with
the addition of the SAE [Fig. 1(c)].
4.2. Wettability analysis
The influence of stearic acid content on the surface CA of the
SAE modified CM samples was investigated and the result was
depicted in Fig. 4(a). One can see that with the increase of stearic
acid content from 0 wt% to 1.0 wt%, the CA of the CM surface
increases sharply. However, when SA content continues to increase
from 1.0 wt% to 2.0 wt%, the CA of CM surface does not change
much. In addition, the surface SA of the CMs samples with stearic
acid content ranging from 0 wt% to 0.8 wt% cannot be measured
because the water droplets on the CM surface do not roll or slide
even if the sample is rotated 180°. When the stearic acid content
is 1.0% or more, the water droplets on the sample surface begin
to slide at a large inclination angle, and the SA of the sample
surface is further lowered as the stearic acid content increases.
After testing the flexural strength of the CMs [size
40 mm  40 mm  160 mm], a newly exposed surface, i.e. frac-
tured surface, is formed. The unmodified CM surface is hydrophilic,
with a water CA of 52.7° [Fig. 4(b), SA is not measurable]. Its
interior is also hydrophilic [see Fig. 4(c)]. However, the stearic acid
(1.0 wt% by cement weight) modified CM possesses hydrophobic-
ity, as shown in Fig. 4(d) and (e). The as-prepared surface and
the newly exposed interior surface exhibit water CA of 130.7°
and 131.1° respectively, which demonstrates the integral
hydrophobicity of the SAE modified CM [also see the Supporting
Material (SM), Movie S1]. The CM specimen modified with 1.0 wt
% stearic acid was used for further characterization and
 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678 5

measurement. The unmodified and modified CM were abbreviated adsorption and/or calcium stearate on the fractured surface of
to UCM and MCM respectively. the sample. In addition, it can be observed in the C 1s spectra that
a main peak centred at 284.7 eV and two weak peaks located at
289.5 eV and 288.7 eV respectively for the MCM. The peak located
at 289.5 is derived from CaCO3 and the peak located at 288.7 eV
can be attributed to the COOR group of calcium stearate [22]. How-
ever, the signal of the COOR group was not detected by XPS of the
unmodified CM sample. In addition, compared with the UCM, the
intensity of C1S peak of MCM increases [Fig. 5(h)], while the inten-
sity of O 1S peak decreases [Fig. 5(h)]. This can be explained by the
fact that calcium stearate formed on the surface of the MCM, which
increases the carbon content and reduces the oxygen content of
the surface.

4.4. Pore structure analysis

Movie S1.
4.3. Surface morphologies and XPS analysis
The FE-SEM images of the fractured surfaces of different CM
samples were shown in Fig. 5(a)–(f). It was observed from Fig. 5
(a) and (b) that the internal structure of the UCM is compact at
lower magnification (i.e., 200 and 1000). However, a large num-
ber of voids are observed under the same magnification on the
fractured surface of the MCM, which indicates that the introduc-
tion of SAE makes the structure of hardened CM loose. At high
magnification, the rough surfaces of both samples can be observed
from Fig. 5(c) and (f). The surface is composed of micron-sized
irregular particles, acicular crystals, aggregates and other cement
hydration products of various shapes [see Fig. 5(c) and (f)]. There
are many pores between cement hydration products, and the pores
in Fig. 5(c) are larger than those in Fig. 5(f). It is generally believed
that the wettability of solid surface is determined by both surface
chemistry and surface microstructures. Therefore, the surface
chemical compositions of the UCM and MCM were analyzed using
XPS, and the results are shown in Fig. 5(g)–(i). The XPS spectrum
shows the presence of elemental oxygen, carbon, calcium and sili-
con on both the fractured surfaces of the UCM and MCM. Elemental
oxygen, calcium and silicon are derived from cement hydration
products. Elemental carbon is derived from carbonization, carbon
The MIP measurement results of the UCM and MCM specimens
were depicted in Fig. 6. Fig. 6(a) shows the pore volume of the UCM
and MCM as a function of pore diameter. It is observed that the
total pore volume of the UCM and MCM are 0.0425 and
0.0770 ML/g, respectively. Therefore, the addition of SAE increases
the voids of the CM. Fig. 6(b) shows the percentage of voids in a
specific range of the MCM and UCM obtained from MIP measure-
ment. One can see from Fig. 6(b) that the percentage of smaller
pores with pore diameter less than 10 nm and within the range
of 10–100 nm in the UCM are 3.12% and 67.09%, respectively.
The percentage of larger pores in the UCM are 25.64% (102–
103 nm), 3.75% (103  104 nm) and 0.4% (104–105 nm), respec-
tively. Comparing the percentage of pores volume between the
MCM and the UCM, it can be concluded that the MCM has a
reduced micropore volume content and an increased macropore
volume content. In other words, the compactness of the CM mod-
ified by SAE is reduced. The threshold pore diameter is another
important parameter to investigate the pore structure of cement
based materials. The critical pore size is defined as the maximum
pore size corresponding to a significant increase in the volume of
mercury intruded [23]. The threshold pore diameter of the MCM
(304 nm) is visibly higher than that of the UCM (59 nm), indicating
higher connectivity of the pores. The results of MIP test are in good
agreement with those of SEM observation. In summary, the modi-
fication of SAE increases the total pore volume, the pore size and
the pore connectivity of the CM [24].

Fig. 4. (a) Influence of stearic acid content on the surface CA of the SAE modified CMs. (b) image of water droplets on the as-prepared surface of the CM without using SAE and
the inset shows a surface CA is about 52.7°; (c) image of water droplets on the fractured surface of the CM without using SAE and the inset shows a surface CA is about 0°; (d)
image of water droplets on the as-prepared surface of the CM modified with 1.0 wt% SA and the inset shows a surface CA is about 130.7°; (e) image of water droplets on the
fractured surface of the CM modified with 1.0 wt% SA and the inset shows a surface CA is about 130.7°.
6 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678

Fig. 5. (a–c) FE-SEM images of the fractured surface of the UCM at different magnification, (a) 200; (b) 1000; (c) 10,000; (d–f) FE-SEM images of fractured surface of the
MCM at different magnification, (d) 200; (e) 1000; (f) 10,000; (g–i) XPS spectra of the MCM, (g) survey spectra; (h) high resolution XPS spectra in C 1s region and (i) high
resolution XPS spectra in O 1s region.

Fig. 6. Pore size distribution of the UCM and MCM specimens measured with MIP. (a) Cumulative intrusion volume; (b) cumulative intrusion volume percentage; (c)
incremental intrusion volume.

4.5. Capillary absorption analysis
The curves of capillary water absorption of the UCM and MCM
as a function of operation time were depicted in Fig. 7. As shown
in Fig. 7, the water absorption of the UCM increases sharply with
the increase of time in the initial 10 h. The water absorption of
the sample increased slowly after 10 h. In contrast, the water
absorption of the MCM increases slowly with the increase of test
time during the whole test period. After the test, the water absorp-
tion of the UCM is 0.2813 g/cm3, while the corresponding water
absorption of the MCM is only 0.0392 g/cm3. The results of capil-
lary water absorption test show that the water absorption of
 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678
Fig. 7. Water absorption of the UCM and MCM as a function of immersion time.
cement mortar can be significantly reduced by 86.06% by using SAE
as modifier. The improved water resistance of the MCM can be
interpreted by the following equation [25]:
P ¼ ð2c=r c Þcos h
where P is the capillary force of water on solid surface, c is water
surface tension (7.280  102 N/m), rc is the radius of the pore in
cement motar, h is the water CA of solid surface (CA = 22.7° and
108.7° on the surfaces of the UCM and the MCM, respectively).
The value of P for the UCM is positive, water droplets on the sample
surface will automatically enter the pores of the UCM. As a compar-
ison, the MCM exhibits a negative value of P [cos (108.7°) is nega-
tive]. As a result, surface water on the MCM is repelled by the
surface. At this case, only under extra pressure can water enter
the pore of the MCM.
4.6. Integral hydrophobicity and its mechanical robustness
The SAE modified CM exhibits high hydrophobicity after hard-
ening, without any additional surface treatment or surface rough-
Fig. 8. Images of water droplets on the surface of the MCM after various mechanical damages. (a) the surface of the as-prepared MCM; (b) the surface of the MCM after being
abraded; (c) the surface of the MCM after the MCM was sawn into two segments; (d) the newly exposed surfaces of the MCM after the MCM was sawn into two segments.
7
ening process. Fig. 8(a) shows water droplets sit on the as-prepared
surface of the MCM. The CA and SA for water are 131.5°and 81.7°,
respectively, which demonstrates the hydrophobicity of the MCM
surface. The surface of the MCM was also hydrophobic after being
polished using 280 # sandpaper, with a CA of 147.2° and SA of
55.6° [also see SM, Movie S2]. The CA of the polished surface does
not decrease, but increases significantly, which can be explained by
the following Wenzel equation [26]:
ð5Þ
Movie S2.
coshr ¼ r cos h ð6Þ
where hr is the water CA on a rough solid surface, r is roughness factor
and h is the water CA on a smooth solid surface. According to Eq. (6),
as the roughness increases, the CA of hydrophilic surface will
decrease, while the CA of hydrophobic surface will increase. In the
present case, the surface roughness of the MCM is increased after
being abraded, resulting the increase of surface CA. The surface of
the sample was repeatedly scratched with an artistic blade [Movie
S3, SM], or the sample was divided into two parts by a manual saw
[Movie S4, SM]. It was found that the CAs of the damaged surfaces
remained high values (148.5° and 146.3°, respectively). Hence, the
hydrophobicity of the MCM is mechanically robust [27]. In addition,
8 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678

the above results also show that both the surface and the interior of
the CM modified by SAE are hydrophobic. In other words, the MCM
possesses integral hydrophobicity. Compared with other hydropho-
bic modification methods of concrete, the advantages of the SAE
modification method used in this study are as follows: First, it does
not peel off and is resistant to abrasion. Second, after the large crack
is generated, the surface of the crack is still hydrophobic. Third, the
price is much lower than that of the silane.

Fig. 9. Polarization curve measurement of the UCM and MCM.

4.8. Water immersing stability analysis

The long-term contact of hydrophobic concrete with water may

cause degradation of its surface hydrophobicity, which will be
Movie S3. detrimental to the durability of concrete [30]. Fig. 10 shows the
water immersing stability of surface CAs of different MCM sam-
ples. A batch of 15 MCM samples were used for water immersing
stability mearsurement and tap water was used as the immersing
liquid. The top surface (as-prepared surface, also see Fig. 8a) of a
cubic MCM is used as a testing surface, and the bottom surface
after being abraded is used as another testing surface (the abraded
surface, also see Fig. 8b). Every other day, a sample was taken from
the water. The absorbed water on the sample surface is wiped with
a paper towel and the CA of the sample surface is tested. One can
see from Fig. 9 that the CAs of both the as-prepared surface and the
abraded surface of the MCM show a slight decrease with the
increase of immersing time. However, the CAs of both the as-

Table 2
Movie S4. Corrosion parameters obtained from the fitting results of polarization curve.

Sample Icorr (A cm2) Ecorr (V) Rp (ohms)

UCM 3.33  10-4 0.929 147.1
4.7. Polarization curve test MCM 1.09  10-6 0.407 91.36  103

The polarization curve test results of the UCM and the MCM
samples containing steel sheet are depicted in Fig. 9. Compared
with the UCM, the polarization curve of the MCM moves towards
the direction of rightward and downward, which indicates that
the MCM possesses a higher corrosion potential (Ecorr) and a lower
corrosion current density (Icorr). The important corrosion parame-
ters derived from Fig. 9 were depicted in Table 2. Obviously, the
Icorr of the MCM (1.09  106 A cm2) is much lower than that of
the UCM (3.33  104 A cm2), and the Ecorr of the MCM
(0.407 V) is much higher than that of the UCM (0.929 V). In gen-
eral, Icorr is the most important parameter for evaluating the corro-
sion resistance of material [28]. The lower the Icorr, the stronger the
corrosion resistance of the material. In addition, corrosion resis-
tance (Rp) is another important parameter to evaluate the corro-
sion resistance of material [29]. As shown in Table 1, the MCM
sample exhibits a much higher Rp (91.36  103) than that of the
UCM sample (147.1). Thus, it can be concluded that the method
of using SAE admixture in cement mortar can significantly improve
the corrosion resistance of steel in the cement mortar against chlo-
Fig. 10. Effect of water immersing time on the surface CA of different MCM
ride ion. samples.
 Z. Feng et al. / Construction and Building Materials 227 (2019) 116678
Fig. 11. Mechanical strength measurement of the UCM and the MCM as a function
of curing ages.
prepared surface and the polished surface were only reduced by
6.08% and 9.51% respectively after 15 days of soaking. In particular,
the CA becomes larger when the soaked surface is polished,
exceeding 140°. Therefore, the MCM prepared in the present work
has stable hydrophobic performance and can withstand long-term
water immersion.
4.9. Mechanical strength analysis
Mechanical strength is the most important parameter when
cement based concrete is used as a structural material. The
mechanical strength of hardened Portland cement increases with
age. In one month, the mechanical strength increases rapidly,
and it can be further increased in the later period. In the present
case, the compressive strength and the flexural strength of the
UCM and the MCM were measured at different ages and the results
were shown in Fig. 11. It can be observed that the compressive
strength and the flexural strength of both the UCM and the MCM
increase with the growth of age. The compressive strength and
the flexural strength of the MCM are obviously lower than that
of the UCM at the same age. At 90 days of age, the compressive
strength and flexural strength of the MCM are 36.25 MPa and
8.16 MPa, respectively. Compared with the UCM of the same age,
the compressive strength is reduced by 16.2% and the flexural
strength is reduced by 20.0%. Song et al. prepared a superhy-
drophobic concrete sample using fluoroalkylsilane (FAS) as cement
admixture [2]. Both of the compressive strength and the flexural
strength of the modified concrete reduced about 40% compared
with that of the unmodified concrete. In contrast, the mechanical
strength reduction of the SAE modified sample in this work is
much smaller.
5. Conclusions
The SAE modified CMs (MCMs) were prepared by adding the
hydrophobic admixture, i.e., SAE, into the CMs during their fabrica-
tion process. The adding of SAE into the CP resulted in the reduc-
tion of the fluidity and the setting time, but led to the increment
of the SCWC. The CM modified exhibited integral hydrophobicity.
Both the surface and the inner surface of the MCM were hydropho-
bic and have water CAs larger than 130°. The hydrophobic MCM
was mechanical robustness and maintained its hydrophobicity
after being abraded, cut and scratched. The MCM showed very
low water absorption and improved corrosion resistance to Cl- in
comparison with the control sample. The compressive strength
and flexural strength of the MCM were 16.2% and 20.0% lower than
the control sample, respectively. However, their absolute values
9
were still high, which were 36.25 MPa and 8.12 MPa, respectively.
The stearic acid modified cement mortar presented in this work
might find large applications in waterproof concrete and
chloride-resistant concrete due to its low cost.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors acknowledge with pleasure the financial sup-
port of this work by the National Natural Science Foundation of
China (Grant No. 51263018).
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