Construction and Building Materials 241 (2020) 118015

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Construction and Building Materials

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Influence of various bentonites on the mechanical properties and

impermeability of cement mortars
Liu Mengliang a, Hu Yang b, Lai Zhenyu a,⇑, Yan Tao a, He Xin a, Wu Jie a, Lu Zhongyuan a, Lv Shuzhen a
a
Southwest University of Science and Technology, School of Materials Science and Engineering, State Key Laboratory of Environmental-Friendly Energy Materials, Mianyang,
Sichuan 621010, China
b
Sichuan Huashi Green Homeland Building Materials Co. Ltd., Chengdu, Sichuan 610081, China

h i g h l i g h t s

Various bentonite on the properties of fresh cement mortar was studied.

Magnesium bentonite has the best waterproof and impermeability of cement mortar.

The mechanism of bentonite to the impermeability of cement mortar was discussed.

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

Article history: The durability of cement mortar depends mainly on its impermeability properties. In this study, three dif-
Received 30 August 2019 ferent types of bentonite—sodium bentonite (Na-bent), calcium bentonite (Ca-bent), and magnesium
Received in revised form 18 December 2019 bentonite (Mg-bent)—were added to a cement mortar at different proportions to investigate their effect
Accepted 2 January 2020
on the mortar strength and impermeability. The results show that the three types of bentonite provide a
significant improvement in the performance of cement mortar, and with increasing bentonite content,
this effect is increasingly obvious. For samples with a bentonite content of 10 wt%, the improvement
Keywords:
in compressive strength, flexural strength, and permeability with Na-bent can reach 77.5%, 54.5%, and
Bentonite
Cement mortar
115.7%, respectively; the corresponding improvements with Ca-bent can reach 62.2%, 47.9%, and
Strength 101.9%, while those with Mg-bent can reach 71.6%, 52.2%, and 137.3%, respectively. The waterproofing
Impermeability performance of cement mortar containing Mg-bent is the best, with a maximum impermeability pressure
2.37 times that of the reference group, followed by Na-bent, and finally Ca-bent; however, the lowest
impermeability pressure is also 2.02 times that of the reference group. In general, the addition of ben-
tonite improved the strength and impermeability of the cement mortar and has potential application
value for improving the durability of cement mortars.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction consisting primarily of montmorillonite. Its chemical composition

Cement mortar is made by mixing fine aggregate and water in a
particular proportion, resulting in a heterogeneous and porous
composite material. However, the pore structure of cement mortar
can cause leakage in buildings, and the migration of water in the
pore structure can introduce harmful ions such as CO2, Cl, and
SO2
4 that can cause chemical damage to the structure [1–3].
Reducing the permeability of the cement mortar is the primary
method to solve this problem.
Bentonite is currently widely used to improve the performance
of cement mortars. Bentonite is a type of hydrated clay mineral
⇑ Corresponding author.
E-mail address: laizhenyu@swust.edu.cn (Z. Lai).
mainly includes silica, alumina, and water [4,5]. Based on the type
and ratio of the interlayer ions of montmorillonite, bentonites can
be divided into calcium bentonite (Ca-bent), sodium bentonite
(Na-bent), and magnesium bentonite (Mg-bent) [6–11].
Because bentonite has excellent water swelling properties and
is considered non-toxic and harmless, it can be added to mortar
to fill the tiny pores in the mortar and reduce the migration of
water in the pore structure, thus providing excellent waterproofing
and impermeability characteristics [12–15]. Some researchers
have prepared a humidity-adjustable mortar for the automatic
adjustment of indoor humidity [16]. In addition, researchers have
added bentonite to mortar and concrete by replacing part of the
cement. The compressive strength of the replaced sample was sim-
ilar to that of the original sample, and its sulfate attack resistance

https://doi.org/10.1016/j.conbuildmat.2020.118015
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 M. Liu et al. / Construction and Building Materials 241 (2020) 118015

was continuously improved, indicating that bentonite can be used

as a low-cost auxiliary material [17–21]. Bentonite can also be
applied as an impervious waterproofing material. Bentonite
absorbs free water and swells in the mortar, which densifies the
paste, thus reducing the porosity of the mortar; the formation of
more calcium-silicate-hydrate (C-S-H) through the pozzolanic
reaction between bentonite and calcium hydroxide is also benefi-
cial for improving the impermeability of the mortar [22,23]. For
example, in reservoir dams, concrete with high plasticity and low
permeability can be obtained after incorporating bentonite
[24,25]. Studies have shown that the addition of bentonite to the
cement matrix used to cure radioactive waste and heavy metals
can effectively reduce the leaching rate of the radionuclides and
heavy metals [26–28]. While most of the above studies used ben-
tonite, the chemical composition of bentonite in different regions
varies, making it difficult to compare their results. Therefore, based
on an investigation of the influence of bentonite on mortar perfor-
mance, a follow-up study on the effects of different types of ben-
tonite on mortar performance was proposed to facilitate the use
of bentonite to improve the waterproofing performance of mortars
[29]. Fig. 1. Phase composition of bentonites.
In this paper, Na-bent, Ca-bent, Mg-bent, and quartz are mixed
into mortars, and the flexural strength, compressive strength, and
The bentonite phases were determined by X-ray diffraction (PANalytical, X’Pert
impermeability of the resulting mortars are measured. The influ-
Pro, Netherlands; CuKa wavelength = 1.5406 nm, scanning step = 0.02 at 8°/min
ence of the bentonite type on the mortar properties was obtained from 3° to 80°). According to the consistency testing method indicated in Chinese
by comparing the performance of the mortars, and the change in industry standard JGJ/T70-2009, the tip of the test cone of the mortar consistency
the microstructure of the mortars was also considered to explore meter and the surface of the mortar were recorded, the brake screw was loosened,
the mechanism by which bentonite affects the waterproofing and and the screw was immediately tightened to record another reading in 10 s; the dif-
ference between the two readings is the consistency of the mortar. An NLD-3
impermeability of the mortar. cement mortar fluidity tester (Wuxi Jianyi Instrument & Machinery Co., Ltd.) was
used to determine the fluidity of the mortar. The mixed mortar was quickly placed
2. Experiment into the flow test mold in two layers. After flattening the surface, the test mold was
opened and vibrated 30 times within 30 ± 1 s. The maximum diffusion diameter of
2.1. Materials and procedures the mortar was measured, and the diameter perpendicular to that was calculated;
the average value was reported as the fluidity of the mortar. The flexural strength
This study used ordinary Portland cement produced by the Lafarge Shuangma and compressive strength of the mortars were tested according to the Chinese
Cement Plant (Sichuan, China) with an average particle size of about 20 lm. The building materials industry standard JC 474-2008. An SJS-1.5S digital mortar per-
chemical composition is listed in Table 1. Na-bent, Ca-bent, and Mg-bent were sup- meability meter (Wuxi Jianyi Machinery Co., Ltd.) was used to determine the per-
plied by the Shandong Weifang Shengshi Montana Stone Technology Co., Ltd. The meability of the mortar. The cured samples were removed after the surface had
average particle size is approximately 10 lm. The phase composition and chemical dried, and the samples were sealed with a mixture of paraffin and grease and placed
composition are presented in Fig. 1 and Table 1. The purity of the standard sand in a permeation apparatus for the water permeability test. The water pressure starts
used is 98%, and the fineness modulus is 2.93. The quartz used is ground from at a constant pressure of 0.2 MPa for 2 h, after which the pressure is increased by
ordinary quartz sand, and its average particle size is about 10 lm. 0.1 MPa per hour. When three of the six test pieces exhibited water seepage, the
In these experiments, the effects of different bentonite blends on the basic test was stopped, and the corresponding water pressure value was recorded.
properties of ordinary Portland cement mortar mixtures were studied, considering The morphology of the bentonites and their influence on the morphology of the
Na-bent, Ca-bent, and Mg-bent, with quartz as a reference group. Cement mortars mortar hydration products were observed by scanning electron microscopy (SEM;
were prepared according to different dosages of bentonite and quartz. The mixing MAIA3, TESCAN, Czech Republic) and energy-dispersive spectroscopy (EDS;
ratio of the mortar is cement:water: sand = 1:0.79:3.97. The amounts of bentonite OCTANE SUPER, AMETEK, USA). Measurement of the pore structure of the samples
or quartz added are 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, and 10 wt% of the cement is based on mercury intrusion porosimetry (MIP) using a Micromeritics Autopore
content. When preparing the samples, the cement, bentonite, and sand were first IV9500 MIP instrument (Micromeritics Instrument Co. Ltd., USA).
placed into a cement mortar mixer and dry mixed until uniform; water was then
added and the mixture was stirred evenly. Samples were molded at an ambient
temperature of 20 ± 3 and compacted with a vibrating table for 15 s. At the same
3. Results and discussion
time, all samples were covered with plastic sheets to prevent evaporation. After
24 h of curing, the mold was released, and these mortar specimens were cured in 3.1. Workability of cement mortars
water at 20 ± 2 until the specified test age.
The effect of different types and amounts of bentonite on the
2.2. Test methods workability of fresh mortar is shown in Fig. 2. The results show that
Three prisms with dimensions of 160 mm  40 mm  40 mm and 144 circular
the consistency and fluidity of the mortar decreased with an
truncated cones with dimensions of 80 mm  70 mm  30 mm were prepared for increasing amount of bentonite, which is consistent with the
each of the mixtures. results reported in previous studies [30–32]. Comparing the results

Table 1
Chemical composition of bentonites and cement.

Chemical Composition (%)

SiO2 Al2O3 CaO Fe2O3 MgO K2O TiO2 Na2O SO3 other
Ca-bent 64.32 18.24 7.13 3.8 3.68 1.74 0.4 0.31 0.03 0.34
Na-bent 62.62 16.46 5.92 3.26 3.50 1.26 0.34 6.31 0.05 0.27
Mg-bent 66.29 16.70 5.38 3.15 6.34 1.14 0.35 0.33 – 0.33
Cement 19.26 4.33 65.46 3.06 1.60 0.77 – 0.13 4.45 0.94
 M. Liu et al. / Construction and Building Materials 241 (2020) 118015 3

absorption effect of quartz on the water is only due to its wetting

effect on the surface, and thus it does not have a significant impact
on the performance of the mortar. The water swelling effects of Ca-
bent, Na-bent, and Mg-bent are shown in Fig. 3. It can be seen that
Na-bent has the strongest water absorption, while the water
absorption of Mg-bent and Ca-bent are similar and weaker than
that of Na-bent. This is because the Na+ charge is low, and the force
of the crystal layer is weak. Under hydration, the interlayer of Na-
bent can easily spread or even be peeled off, resulting in a strong
swellability. In contrast, Mg2+ and Ca2+ have larger charges and
the same size, and thus attraction effect between the layers is sig-
nificant. As a result, the distance between the layers of Mg-bent
and Ca-bent is small, and thus their ability to absorb water is lim-
ited. The difference in water swellability of the three bentonites
resulted in a large loss of workability in the mortar containing
Na-bent, while the effects of Mg-bent and Ca-bent were compara-
ble and relatively small. It is worth noting that the consistency of
the mortar with 10% Na-bent was reduced to 72 mm. If the dosage
is increased further, it will cause difficulty in mortar preparation.

3.2. Strength of cement mortars

The effect of different amounts of bentonite and quartz on the

flexural strength of cement mortars is shown in Fig. 4. The results
show that bentonite has a positive effect on the flexural strength of
the mortar, and the overall trend shows that the flexural strength
of the mortar gradually increases with increasing amount of ben-
tonite in the mortar. Compared with the addition of quartz with
the same particle size distribution, it can be found that the varia-
tion in the flexural strength of the quartz samples is small within
the range of added contents in this study.
Fig. 5 shows the effect of addition of 10 wt% Ca-bent, Na-bent,
Mg-bent, and quartz on the flexural strength of the mortar. The
results indicate that the 7-d flexural strengths of samples with
10 wt% addition of Ca-bent, Na-bent, Mg-bent, and quartz
Fig. 2. Effect of bentonites on mortar performance: (a) consistency; (b) fluidity.
increased by 42.1%, 54.5%, 41.2%, and 21.8%, respectively, while
the 28-d flexural strength increased by 47.9%, 54.5%, 52.2%, and
13.6%, respectively, compared to those of the blank sample. Thus,
Na-bent had the most obvious effect on the flexural strength of
for the three types of bentonite, Na-bent had the most significant
the mortar. Moreover, the flexural strengths of the Mg-bent and
influence on the workability of the mortar. When 2, 4, 6, 8, and
10 wt% Na-bent was added to the mortar, its consistency decreased
from 103 mm to 93, 95, 87, 79, and 72 mm, respectively; in other
words, the maximum consistency decreased by 29.7% with the
addition of 10 wt% Na-bent. The fluidity of the mortar with added
2, 4, 6, 8, and 10 wt% Na-bent decreased from 247 mm to 234, 240,
Na-bent
Mg-bent

Ca-bent

230, 221, and 207 mm, respectively, representing a decrease from

the maximum value of 16.3%. The effect of adding Mg-bent on the
mortar consistency was similar to that of Ca-bent. When the
dosage was 10%, the mortar consistency was 80 mm and 83 mm,
representing decreases of 22.3% and 19.4%, respectively. When
the dosage was 6%, the effects of Mg-bent and Ca-bent on the flu-
idity of the mortar differed, but their effects were relatively similar
under the other conditions. When the dosage was 10%, the fluidity
of the mortar decreased to 221 mm and 225 mm with the addition
of Mg-bent and Ca-bent, respectively, corresponding to decreases
of 10.6% and 9.0%. Furthermore, quartz with the same particle size
as the bentonite had little effect on the working performance of the
fresh mortar; however, as the dosage increased, the consistency
and fluidity also exhibited a decreasing trend. When the quartz
dose was 10%, the consistency and fluidity decreased by 8.3% and 46mm
4.9%, respectively.
Owing to the strong water absorption of bentonite, the ben-
tonite will absorb water during mixing of the cement mortar, caus- 8mm 6mm
ing the amount of water in the fresh mortar to decrease, which
results in decreased mortar consistency and fluidity. But the Fig. 3. Water swelling of bentonites.
4 M. Liu et al. / Construction and Building Materials 241 (2020) 118015
Fig. 4. Effect of different cement replacement amounts on the flexural strength of
mortar: (a) Ca-bent; (b) Na-bent; (c) Mg-bent; (d) quartz.
Ca-bent mortars are similar at 7 days; however, at 28 days, the
flexural strength of the Mg-bent mortar is significantly higher than
Fig. 5. Effect of different bentonites on the flexural strength (10 wt% addition).
that of the Ca-bent mortar. This indicates that Mg-bent can more
effectively promote the development of the late flexural strength
of the mortar.
The effect of different bentonite and quartz contents on the
compressive strength of the mortar is shown in Fig. 6. The results
show that the influence of bentonite addition on the compressive
strength of mortars is similar to that of the flexural strength. With
increasing bentonite content, the compressive strength of mortar
also exhibits an increasing trend, while the amount of quartz
added has a lesser effect on the compressive strength.
The effect of different bentonites on the compressive strength of
the mortar is shown in Fig. 7. When 10 wt% Ca-bent, Na-bent, Mg-
bent, and quartz are added to the mortar, the 7-d compressive
strengths can be increased by 46.1%, 63.8%, 49.2%, and 20.3%,
respectively, while the 28-d compressive strength can be increased
by 62.2%, 77.5%, 71.6%, and 9.3%, respectively compared to the
blank sample. This indicates that the bentonite has a positive effect
on the development of the later strength of the mortar, and the
effect of Mg-bent is most obvious. At the early age, the increase
in the compressive strength with Mg-bent is close to that with
Ca-bent; however, at 28 days, the strength of the Mg-bent mortar
is significantly higher than that of the Ca-bent mortar. Of the three
types of bentonites, Na-bent also has the most significant effect on
improving the mortar compressive strength.
3.3. Impermeability of the cement mortar
The cement mortars were measured with a step-by-step pres-
sure method to determine the waterproofing ability and imperme-
ability of the mortars. According to the requirements of Chinese
building materials industry standard JC 474-2008, mortar test
blocks with dimensions of 70 mm  80 mm  30 mm were pre-
pared for the mortar impermeability tests, and the impermeability
pressure was tested after 28 d of standard curing. The imperme-
ability pressure values for the mortar samples with the addition
of bentonites and quartz are listed in Table 2. The results indicate
that the impermeability pressure of the mortar increases by 9.8%,
19.6%, 54.9%, 68.6%, and 101.9% with the addition of 2, 4, 6, 8,
and 10 wt% Ca-bent, respectively. Correspondingly, with the addi-
tion of Na-bent the impermeability pressure increases by 17.6%,
35.3%, 56.9%, 76.5%, and 115.7%, respectively, and with the addition
of Mg-bent, the impermeability pressure increases by 35.3%, 43.1%,
80.4%, 115.7%, and 137.3%, respectively. In general, the effects of
the three types of bentonite on the impermeability of the mortar
after 28 d of curing are very apparent. The greater the amount of
 M. Liu et al. / Construction and Building Materials 241 (2020) 118015
Fig. 6. Effect of the bentonite or quartz content on the compressive strength of
mortars: (a) Ca-bent; (b) Na-bent; (c) Mg-bent; (d) quartz.
bentonite added, the greater the improvement in the impermeabil-
ity will be. When 10 wt% bentonite is added to the mortar, the
5
Fig. 7. Effect of different bentonites on the mortar compressive strength (10 wt%
addition).
minimum impermeability pressure of the mortar can be increased
to more than double that of the reference group. Of the bentonites,
Mg-bent has the best water resistance, followed by Na-bent, and
finally Ca-bent.
A linear regression analysis between the bentonite content and
the impermeability pressure reveals that there is a good linear
relationship between these parameters. As shown in Fig. 8, the lin-
ear relationship for Mg-bent is the strongest, with R2 = 0.9780; fol-
lowed by Na-bent, R2 = 0.9699; and finally, calcium-based
bentonite, R2 = 0.9437. These linear correlations provide good
quantitative relationships between the amount of bentonite added
and the impermeability of the mortar. The slope of the fitted line
between the Mg-bent content and impermeability pressure is
k1 = 0.0702; the slope of the fitted line for Na-bent is
k2 = 0.0565; the slope of the fitted line for Ca-bent is k3 = 0.0525.
This indicates that for the same proportion of bentonite added to
the mortar, the impermeability of the mortar is increased to a cer-
tain extent, and the required amount of bentonite to achieve the
same increase in impermeability follows the order Ca-bent > Na-
bent > Mg-bent. Therefore, the use of a smaller amount of Mg-
bent allows the mortar to achieve superior water resistance.
For the reference group, the addition of quartz powder provides
a certain enhancement of the impermeability of the mortar, but its
effect is weaker than that of the bentonites. This indicates that the
improvement in the impermeability of the bentonite mortars is not
only due to the filling of pore spaces by the particles, but also due
to the properties of the bentonite itself.
3.4. Microstructure of the cement mortar
Scanning electron microscopy and EDS analyses were used to
observe the morphology of bentonite in the hydration products
and its influence on the morphology of the hydration products. It
can be seen from Fig. 9 that there are many needle-like phases
on the surface of Na-bent. EDS analysis reveals that these needle-
like products may be a C-S-H gel, and the amorphous product on
the surface of the bentonite is C-A-S-H gel, which has a higher con-
tent of Al and Si. The surface of bentonite has many unsaturated
chemical bonds (Al-O or Si-O), and these chemical bonds can serve
as origin sites for the growth of hydration products during the
hydration process of cement, thus promoting the growth of hydra-
tion products there. The hydration products have an obvious
refinement effect on the pores, and the needle-like hydration prod-
ucts on the surface can be oriented and grow along the direction of
6 M. Liu et al. / Construction and Building Materials 241 (2020) 118015

Table 2
Area2
Impermeability pressure of mortars (MPa). a
Ca-bent Na-bent Mg-bent Quartz
0% 0.51 0.51 0.51 0.51
2% 0.56 0.60 0.69 0.53
4% 0.61 0.69 0.73 0.55
6% 0.79 0.80 0.92 0.56
Spot1
8% 0.86 0.90 1.10 0.61
10% 1.03 1.10 1.21 0.63 Area3
Area1

Fig. 8. Linear relationship between the bentonite content and impermeability

pressure.

the pores. In addition, there is a phenomenon of overlapping with

the surrounding hydration products, which has a specific effect on
the strength of the mortar. It can be seen from Figs. 10 and 11 that
there is no formation of needle-like hydration products on the sur-
face of the Ca-bent or Mg-bent mortars; only amorphous hydration
products can be observed on their surfaces. Owing to the larger
ionic valences of Ca2+ and Mg2+, the attraction effect on the crystal
layer is also significant, making it difficult for the crystal layers to
be stretched, thus limiting the growth of hydration products there.
In addition, it can be seen that the bentonite particles are located at
the large pores in the hydration product, allowing the particles to
effectively fill the pores, thereby hindering the transport of water
in the pores and enhancing the impermeability and strength of
the mortar. Fig. 12 shows that the quartz particles can also act to
fill the pores in the mortar matrix. As the quartz is inert, it will
not participate in the hydration process of the cement, and thus
there is no formation or enrichment of the hydration product,
and the improvement in the mortar strength and impermeability
is also weak. For the needle-like products around quartz particles,
the results of a large number of literature investigation and prelim-
inary experiments show that it is mainly ettringite formed by
cement hydration [33–36].
3.5. Pore structure of the cement mortars
The impermeability and strength properties of cement-based
materials are mainly related to the pore volume and pore structure
characteristics of the material. MIP was used to determine changes
in the pores inside the mortar. The size of the pores and the pressure
at which the mercury is injected can be calculated with Eq. (1); the
volume of mercury injected can represent the volume of the pores.
4ccosh
D¼
P the porosity of the mortar and refine the pore size. The porosity of
Fig. 9. Micromorphology of Na-bent in the mortar after 28 d of hydration: (a)
micromorphology; (b) EDS analysis.
where D is the equivalent pore diameter, c is the surface tension of
mercury, h is the contact angle between the mercury and solid, and
P is the pressure required for mercury injection.
The MIP tests were carried out after the samples had cured for
28 d. The pore size distribution is shown in Fig. 13, and the porosity
of the mortars is listed in Table 3. Fig. 13(a) shows that Ca-bent
decreases the integral curve of the mortar pore volume with the
pore diameter, and the greater the amount of Ca-bent added, the
more obvious this downward trend will be, which indicates a
reduction in the pores in the mortar and a smaller pore size. When
the content of Ca-bent was 4 wt% and 8 wt%, the porosity of the
mortar decreased from 27.16% to 25.63% and 24.59%, respectively.
The main peak of the differential curve is shifted slightly to the left,
which also indicates that the pore structure of the mortar has been
refined to some extent. From the above analysis of the microstruc-
ture of bentonite in the mortar, it can be found that the surface of
Ca-bent can generate more amorphous hydration products, which
reduces the pore space in the mortar, and thus the strength of the
mortar containing Ca-bent is higher than that of the reference
group.
Fig. 13(b) shows that when Na-bent is added to the mortar, the
integral curve of the pore volume with pore size also exhibits a
downward trend, and the extent of the decrease is larger than that
with Ca-bent, indicating that Na-bent can more effectively reduce
ð1Þ
 M. Liu et al. / Construction and Building Materials 241 (2020) 118015
a a
Fig. 10. Micromorphology of Ca-bent in the mortar after 28 d of hydration: (a)
micromorphology; (b) EDS analysis.
the mortars mixed with 4 wt% and 8 wt% Na-bent decreased from
27.16% to 24.87% and 22.58%, respectively. At the same time, the
leftward shift of the main peak of the differential curve is much lar-
ger with Na-bent than Ca-bent. This also indicates that Na-bent has
a stronger effect on the pore refinement of the mortar. From the
analysis of the micromorphology, Na-bent in the mortar matrix
can not only form amorphous hydration products on the mortar
surface, but can also form acicular hydration products oriented
toward the pores. This causes the porosity of the Na-bent mortar
to decreases more significantly than that of the Ca-bent mortar,
and thus the effect of Na-bent on the mortar strength is also
greater than that of Ca-bent.
Fig. 13(c) that the variation in the integral curve of the pore vol-
ume for Mg-bent mortar is similar to that of the Na-bent mortar,
indicating that Mg-bent can also effectively reduce the porosity
of the mortar and refine the pore structure. When 4 wt% and
8 wt% Mg-bent is added to the mortar, the porosity of the mortar
can be reduced from 27.16% to 25.11% and 22.81%, respectively,
which is equivalent to the results obtained with addition of Na-
bent. Analysis of the micromorphology of Mg-bent in the mortar
indicates that the microstructure of Mg-bent is similar to that of
Ca-bent; hydrated products are only formed on the surface, and
there is no formation of acicular hydration products along the
pores to reduce the porosity of the mortar further. However,
Mg2+ between the Mg-bent layers forms Mg(OH)2 crystals around
7
Fig. 11. Micromorphology of Mg-bent in the mortar after 28 d of hydration: (a)
micromorphology; (b) EDS analysis.
the bentonite through ion exchange, and ability of these crystals
to fill the pores causes the Mg-bent mortar to also have a low
porosity[37,38]. This is a reasonable explanation for the above
trends in the effects of different types of bentonite on the mortar
strength and impermeability. The effects of Mg-bent and Na-bent
on the porosity of the mortar are similar, and thus their strength
properties at the 28-d age are also similar. However, at 7 d of aging,
the compressive strength and flexural strength of Mg-bent are sim-
ilar to that of Ca-bent and significantly weaker than that of Na-
bent, which may be due to the slow exchange between Mg2+ in
Mg-bent and Ca2+ in the hydration product pore solution. There
is not a large amount of Mg(OH)2 crystal formation at 7 d of aging.
In addition, because the surface of Mg-bent is similar to that of Ca-
bent, the formation of hydration products is less than that of Na-
bent, and the porosity is larger than Na-bent; thus, the strength
of the Mg-bent mortar is lower at 7 d. In the later process, with
the progress of ion exchange and the formation of Mg(OH)2 crys-
tals, the porosity of the mortar containing Mg-bent decreases
rapidly, while the strength performance in the later stage increases
rapidly. Although the porosity of the mortars containing Mg-bent
and Na-bent is similar, the impermeability pressure of the Mg-
bent mortar is higher than that of the Na-bent mortar, mainly
due to the formation of flake-like Mg(OH)2 crystals, which can
increase the degree of tortuosity of the water permeation path in
the pores of the mortar.
8 M. Liu et al. / Construction and Building Materials 241 (2020) 118015

Fig. 12. Micromorphology of quartz in the mortar after 28 d of hydration: (a)

micromorphology; (b) EDS analysis.

Fig. 13(d) shows that after incorporating quartz with a similar

particle size to bentonite, the pore volume of the mortar changes
little with the change in the pore diameter, indicating that the
influence of quartz particles on the porosity of the mortar is small.
After the incorporation of 4 wt% and 8 wt% quartz, the porosity of
the mortar is 27.54% and 26.72%, respectively, which is very close
to the 27.16% of the blank group. At a quartz content of 4 wt%, the
porosity even increased slightly, although this increase of only
0.38% may be the result of instrumental errors. It can be seen from
the differential curve that quartz has a certain refinement effect on
the pore structure of the mortar.
The permeability resistance of cement-based materials is deter-
mined not only by the overall porosity, but also by the characteris-
tics of the pore structure. The addition of bentonite leads to the
refinement of the pore structure, but is represented by a differen-
tial curve of the pore volume as a function of pore size. There is no
specific data to describe this phenomenon. To understand the
refinement effect of bentonite on the pore structure of the mortar
more clearly, the full pore size range in the mortar (the pore size
range of the MIP instrument used in the analysis is 6 nm to Fig. 13. Pore size distribution of mortars: (a) Na-bent; (b) Ca-bent; (c) Mg-bent; (d)
360 lm) is divided into four different pore sizes categories: 6– quartz.
50 nm are classified as harmless or less harmful; 50–200 nm are
harmful pores; 0.2–1 lm and 1–360 lm are also harmful pores.
The volume fraction of pores (c) is also used to express the propor- The variation in c is used to understand the effect of bentonite on
tion of pores with different pore sizes in the whole pore size range. the refinement of mortar pores. The effects of different types of
 M. Liu et al. / Construction and Building Materials 241 (2020) 118015
Table 3
Mortar porosity (%).
Adding content (wt%) Ca-bent
0 27.16
4 25.63
8 24.59
bentonite and similarly sized quartz particles on the volume frac-
tion (c) of pores with different pore sizes in the mortar is shown
in Fig. 14.
Fig. 14 indicates that the effect of bentonite on the refinement
of the pores of the mortar is mainly reflected in a decrease in
macropores and increase in small pores. When 8 wt% Ca-bent,
Na-bent, Mg-bent, and quartz were added to the mortar, the pore
volume fraction, c6–50 nm, of the less harmful or harmless pores
in the mortar increased by 12.3%, 17.5%, 11.5%, and 10.8%, respec-
tively, at 28 d of curing; the pore volume fraction of harmful pores,
c50–200 nm, changed little; the pore volume fraction of the multi-
pore pores with sizes of 0.2–1 lm, c0.2–1 lm, increased by 6.4%,
13.3%, 18.1%, and 0.1%, respectively; and the volume fraction of
the multi-pore pores with sizes of 1–360 lm, c1–360 lm,
decreased by 17.5%, 29.6%, 28.2%, and 9.1%, respectively. The pores
in the cement hydration products are caused by the evaporation of
free water during the hydration process. Because bentonite has a
strong water absorption capacity, its water absorption during the
mortar mixing process reduces the amount of free water in the
fresh mortar, thereby reducing the gap between the cement parti-
cles during the hydration process. As a result, the pores in the
hydration product are smaller, and the data shows an increase in
the c6–50 nm fraction and a decrease in the c1–360 lm fraction.
In addition, through the above description of the micromorphology
of bentonite in the mortar, it can be seen that the bentonite will
release absorbed water during hydration of the mortar to form
pores of approximately 1 lm at the junction of the bentonite and
the matrix. Thus, the analysis of the change in the pore volume
fractions of different pore sizes has also been effectively verified.
With the incorporation of bentonite, the c0.2–1 lm fraction exhi-
bits a certain increase.
Na-bent has the best water absorption capacity, and its effect on
the refinement of the pores of the mortar is also the most signifi-
cant. The pore volume fraction of the less harmful or harmless
pores, c6–50 nm, is the largest in the Na-bent mortar, and thus
Fig. 14. Volume fraction of pores with different pore sizes in the mortars (8 wt%
addition).
9
Na-bent Mg-bent Quartz
27.16 27.16 27.16
24.87 25.11 27.54
22.58 22.81 26.72
the permeability resistance of the mortar can improve signifi-
cantly. Ca-bent has a weak water absorption capacity, and thus
its ability to refine the pores of the mortar is also weak. The
increase in the c6–50 nm fraction is only 12.3% with Ca-bent,
and the increase in the corresponding c0.2–1 lm fraction is also
low, only 6.4%. The water absorption capacity of Mg-bent is com-
parable to that of Ca-bent, and thus the increase in the c6–
50 nm fraction of the Mg-bent mortar is also only 11.5%. However,
the c0.2–1 lm fraction of the mortar doped with Mg-bent is larger
than that with the other types of bentonite, indicating that a 2–
3 lm sheet of Mg(OH)2 crystals is formed in the macropores
around the bentonite, and thus the macropores are refined into
pores with sizes between 0.2 lm and 1 lm.
Quartz is inert during the hydration process of the mortar, but
because its particles can fill the pores in the mortar, it can convert
a small number of harmful pores with sizes of 1–360 lm into less
harmful or harmless pores with sizes of 6–50 nm, thereby increas-
ing the impermeability pressure of the mortar. It can be seen that
the bentonite particles of the same size also have the function of
filling the pores in the mortar to achieve a degree of refinement.
In addition, it is worth noting that the pore volume fraction of
the harmless or less harmful pores of the mortar, c6–50 nm, after
adding quartz, Ca-bent, and Mg-bent with equal grain sizes is
25.4%, 26.8%, and 26.0%, respectively; the three are almost equal.
However, the impermeability pressure pressures of Ca-bent and
Mg-bent are much higher than that of quartz with an equal particle
size. In particular, the highest impermeability pressure of Mg-bent
is 1.92 times that of the quartz mortar sample with the same
dosage.
3.6. Mechanism for the effects of bentonite on the cement mortar
Through the discussion of a series of macroscopic properties of
bentonite mortars combined with the influence of bentonite on the
microstructure of mortar hydration products, the following mech-
anism by which bentonite improves the waterproofing effect of
cementitious materials has been proposed. This section will
explain the waterproofing mechanism of bentonite from two per-
spectives: the influence of bentonite on the hydration process of
cement-based materials, and the effect of bentonite when water
passes through the pores. Fig. 15 shows the effect of bentonite
on the hydration of the mortar and the infiltration of water into
the pores. As Fig. 15 shows, the bentonite in the fresh mortar can
absorb some of the free water, thus expanding the volume of the
bentonite. At the same time, the gap between the unhydrated
cement particles and the amount of free water are also reduced rel-
ative to the unblended bentonite, which leads to smaller pore sizes
in the formed hydration products, expressed as the harmless or
less harmful pores(Fig. 14). In addition, the surface of the bentonite
in the cement hydration products can generate a large number of
amorphous or needle-like hydration products, which can reduce
the pore space in the matrix, thereby enhancing the impermeabil-
ity to water of the cement-based material. The water-expanded
bentonite gradually releases the absorbed water as the humidity
in the mortar decreases, causing the volume of the bentonite to
shrink, and forming micron-sized harmful pores between the ben-
tonite and the matrix. However, when external water penetrates
10 M. Liu et al. / Construction and Building Materials 241 (2020) 118015

(a) (b) (c)

Free water between particles Pore

Cement granule Hydrated slurry Outside water

(d) (e) (f)

Quartz particles

(g) (h) Bentonite surface (i)

hydration product

Swelling
bentonite
Bentonite in
hydration products Bentonite expands again
with water
Fig. 15. Waterproofing mechanism of bentonite: (a) (b) (c) reference mortar; (d) (e) (f) mortar mixed with quartz; (g) (h) (i) mortar mixed with bentonite.

(a) (b) (c)

Mg(OH)2

Fig. 16. Waterproofing mechanism of modified bentonite: (a) fresh mortar; (b) mortar mixed with Mg-bentonite; (c) water penetration process in pores.

the matrix, the bentonite can re-expand to fill the surrounding
pores, thereby effectively blocking the passage of water through
the pores. As mentioned above, Ca-bent can significantly improve
the waterproofing performance of the mortar compared to the
quartz particles with an equal diameter. However, by comparing
the volume fractions of pores with different pore sizes in the
quartz and Ca-bent mortars, it can be found that the pore volume
fraction of the harmless or less harmful pores is similar. The differ-
ence is that the 0.2–1 lm pores in the Ca-bent mortar increase, and
because these pores are classified as harmful pores, the improve-
ment in the penetration resistance of the cement-based material
does not have a positive effect or even a negative effect. Therefore,
the waterproofing mechanism described above for the re-
expansion of bentonite in the mortar provides a more appropriate
interpretation of the observed phenomena. From this, it can be
concluded that the improvement in the waterproofing and imper-
meability of cement-based materials by bentonite is mainly caused
by the swelling of the bentonite itself.
For Na-bent, because of its stronger water absorption (Fig. 3), it
has a better refining effect on the pores after hydration and can
convert more harmful macropores into harmless or less harmful
pores. In addition, owing to the looser surface of Na-bent particles,
more nucleation sites can be provided for the growth of surface
hydration products; the more hydrated products are formed, the
lower the porosity of the matrix will be(Fig. 9). These two factors
cause Na-bent to have a better influence on the waterproofing
and impermeability of mortar than Ca-bent. In addition, because
quartz is inert and cannot expand, it can only enhance the imper-
meability of the mortar by the act of particles filling the pores
(Fig. 12).
For Mg-bent, its swellability is similar to that of Ca-bent, but its
improvement in the anti-penetration performance of the mortar is
the best among the three bentonites (Table 2, Fig. 8). The effect of
Mg-bent on the hydration of cement-based materials and the pen-
etration of water into the pores is shown in Fig. 16. Owing to the
ion exchange of Mg2+ with Ca2+ in the pore solution of the hydra-
tion products, Mg2+ is exchanged between the layers of Mg-bent.
Thus, Mg(OH)2 crystals are formed under highly alkaline condi-
tions, which generally occur in the form of flakes near the ben-
tonite to create the micromorphology shown in Figs. 16(b), 11.
When external water passes through the pores, the Mg-bent not
only has the water-swelling and waterproofing properties
described above, but the formed Mg(OH)2 crystals can also reduce
the pores and increase the tortuosity of the water permeation path.
Therefore, mortar mixed with Mg-bent can achieve excellent water
resistance under the dual action of Mg-bent and the formed Mg
 M. Liu et al. / Construction and Building Materials 241 (2020) 118015
(OH)2 crystals. Recently, studies have also shown that there is a
pozzolanic reaction between bentonite and calcium hydroxide
[39–41]. The effects of bentonite on the cement mortar were not
only the waterproof mechanism mentioned but also the pozzolanic
reaction consumes part of calcium hydroxide, which generated
more C-S-H and made the matrix more compact.
4. Conclusion
By comparing the effects of different types of bentonite and
quartz on the workability, strength properties, and impermeability
of cement mortars, combined with consideration of the changes in
the microstructure and pore structure of the mortars, the following
conclusions could be drawn:
(1) Bentonite has a significant influence on the workability of
the mortar. The main result is that the consistency and flu-
idity of the fresh mortar decrease with increasing bentonite
content; the loss of mortar fluidity is mainly caused by the
absorption of water by bentonite.
(2) The addition of bentonite or quartz with an equal grain size
can increase the flexural strength and compressive strength
of the mortar; the larger the added amount of bentonite or
quartz, the more obvious the increase will be.
(3) The mortar made with Mg-bent has the best impermeability,
and the maximum impermeability pressure can reach 2.37
times that of the blank group. The impermeability pressure
of the mortar generally increases with increasing bentonite
content and exhibits a strong linear relationship.
(4) Bentonite can refine the pore structure of the mortar; the
increase in micron-sized pores between 0.2 lm and 1 lm
is a characteristic unique to the incorporation of bentonite.
It is worth noting that although Na-bent can provide the mortar
with better impermeability, it has a significant influence on the
workability of the fresh mortar, and Mg-bent can achieve an excel-
lent waterproofing effect with small fluid loss of the mortar.
Author contributions
Lai Zhenyu developed the idea for the study, Liu Mengliang and
Hu Yang analysed most of the data, and wrote the initial draft of
the paper. The other authors contributed to refining the ideas, car-
rying out additional analyses and finalizing this paper.
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.
Acknowledgments
The authors would like to thank the projects supported by the
National Key Research and Development Plan (2016YFC0701004),
Sichuan Science and Technology Program (No.2019ZDZX0024),
Open Fund of Southwest University of Science and Technology
(17FKSY0108, 19FKSY05).
References
[1] J.Y. Yoo, H.S. Lee, Y.J. Kim, Experimental study on the water penetration into mortar
under water pressure condition, Key Eng. Mater. 385–387 (2008) 681–684.
[2] Y. Farnam, C. Villani, T. Washington, M. Spence, J. Jain, W. Jason Weiss,
Performance of carbonated calcium silicate based cement pastes and mortars
exposed to NaCl and MgCl2 deicing salt, Constr. Build. Mater. 111 (2016) 63–
71.
11
[3] J.M. Loche, A. Ammar, P. Dumargue, Influence of the migration of chloride ions
on the electrochemical impedance spectroscopy of mortar paste, Cem. Concr.
Res. 35 (9) (2005) 1797–1803.
[4] B. Meng, Q. Guo, X. Men, S. Ren, W. Jin, B. Shen, Preparation of modified
bentonite by polyhedral oligomeric silsesquioxane and sodium dodecyl
sulfate in aqueous phase and its adsorption property, Mater. Lett. 253
(2019) 71–73.
[5] Additives EPo, Products or Substances used in Animal F. Scientific Opinion on
the efficacy of Bentonite (dioctahedral montmorillonite) for all species. EFSA J
2011;9(6):2276.
[6] M. Segad, B. Jonsson, T. Akesson, B. Cabane, Ca/Na montmorillonite: structure,
forces and swelling properties, Langmuir 26 (8) (2010) 5782–5790.
[7] M.H. Köster, L.B. Williams, P. Kudejova, H.A. Gilg, The boron isotope
geochemistry of smectites from sodium, magnesium and calcium bentonite
deposits, Chem. Geol. 510 (2019) 166–187.
[8] G. Sposito, K.M. Holtzclaw, L. Charlet, C. Jouany, A.L. Page, Sodium-calcium and
sodium-magnesium exchange on wyoming bentonite in perchlorate and
chloride background ionic media, Soil Sci. Soc. Am. J. 47 (1983) 51–56.
[9] L. Liu, Prediction of swelling pressures of different types of bentonite in dilute
solutions, Colloids Surf., A 434 (2013) 303–318.
[10] M. Muzakky, C. Supriyanto, Modification of three types of bentonite with
zirconium oxide chloride (ZOC) of local products using intercalation process,
Indonesian J. Chem. 16 (2016) 14–19.
[11] R. Fernandez, J. Cuevas, U.K. Mader, Modelling concrete interaction with a
bentonite barrier, Eur. J. Mineral. 21 (1) (2009) 177–191.
[12] S. Andrejkovičová, C. Alves, A. Velosa, F. Rocha, Bentonite as a natural additive
for lime and lime–metakaolin mortars used for restoration of adobe buildings,
Cem. Concr. Compos. 60 (2015) 99–110.
[13] P. Leroy, A. Revil, D. Coelho, Diffusion of ionic species in bentonite, J. Colloid
Interface Sci. 296 (1) (2006) 248–255.
[14] H.H. Lee, C.W. Wang, experimental study on cement mortar with bentonite,
Adv. Mater. Res. 671–674 (2013) 1741–1744.
[15] A.K. Parande, B. Ramesh Babu, M. Aswin Karthik, K.K. Deepak Kumaar, N.
Palaniswamy, Study on strength and corrosion performance for steel
embedded in metakaolin blended concrete/mortar, Constr. Build. Mater. 22
(3) (2008) 127–134.
[16] M. Li, Z. Wu, Preparation, characterization, and humidity-control performance
of organobentonite/sodium polyacrylate mortar, J. Macromol. Sci. Part B 51 (8)
(2012) 1647–1657.
[17] J. Mirza, M. Riaz, A. Naseer, F. Rehman, A.N. Khan, Q. Ali, Pakistani bentonite in
mortars and concrete as low cost construction material, Appl. Clay Sci. 45 (4)
(2009) 220–226.
[18] S. Ahmad, S.A. Barbhuiya, A. Elahi, J. Iqbal, Effect of Pakistani bentonite on
properties of mortar and concrete, Clay Miner. 46 (1) (2018) 85–92.
[19] J.P. Gonçalves, L.M. Tavares, R.D. Toledo Filho, E.M.R. Fairbairn, Performance
evaluation of cement mortars modified with metakaolin or ground brick,
Constr. Build. Mater. 23 (5) (2009) 1971–1979.
[20] N. Mesboua, K. Benyounes, A. Benmounah, S.K. Shukla, Study of the impact of
bentonite on the physico-mechanical and flow properties of cement grout,
Cogent Eng. 5 (1) (2018).
[21] I. Garcia-Lodeiro, N. Boudissa, A. Fernandez-Jimenez, A. Palomo, Use of clays in
alkaline hybrid cement preparation. The role of bentonites, Mater. Lett. 233
(2018) 134–137.
[22] F. Raúl, A.I. Ruiz, J. Cuevas, Formation of C-A-S-H phases from the interaction
between concrete or cement and bentonite, Clay Miner. 51 (2) (2018) 223–
235.
[23] J. Wei, B. Gencturk, Hydration of ternary Portland cement blends containing
metakaolin and sodium bentonite, Cem. Concr. Res. 123 (2019) 105772.
[24] M.A. Fadaie, M. Nekooei, P. Javadi, Effect of dry and saturated bentonite on
plastic concrete, KSCE J. Civ. Eng. 23 (8) (2019) 3431–3442.
[25] A.T. Amlashi, S.M. Abdollahi, S. Goodarzi, A.R. Ghanizadeh, Soft computing
based formulations for slump, compressive strength, and elastic modulus of
bentonite plastic concrete, J. Cleaner Prod. 230 (2019) 1197–1216.
[26] I. Plecas, R. Pavlovic, S. Pavlovic, Leaching behavior of 60Co and 137Cs from
spent ion exchange resins in cement–bentonite clay matrix, J. Nucl. Mater. 327
(2) (2004) 171–174.
[27] I. Sato, K. Maeda, M. Suto, M. Osaka, T. Usuki, S. Koyama, Penetration behavior
of water solution containing radioactive species into dried concrete/mortar
and epoxy resin materials, J. Nucl. Sci. Technol. 52 (4) (2015) 580–587.
[28] M. Katsioti, N. Katsiotis, G. Rouni, D. Bakirtzis, M. Loizidou, The effect of
bentonite/cement mortar for the stabilization/solidification of sewage sludge
containing heavy metals, Cem. Concr. Compos. 30 (10) (2008) 1013–1019.
[29] H. Yang, D. Long, L. Zhenyu, H. Yuanjin, Y. Tao, H. Xin, et al., Effects of bentonite
on pore structure and permeability of cement mortar, Constr. Build. Mater.
224 (2019) 276–283.
[30] C.H. Yu, G.H. Li, J.L. Gao, B. Lan, Q. Wei, D.Z. Xu, Effect of bentonite on the
performance of the limestone manufactured-sand mortar, Appl. Mech. Mater.
357–360 (2013) 1374–1378.
[31] A. Kaci, M. Chaouche, P.A. Andréani, Influence of bentonite clay on the
rheological behaviour of fresh mortars, Cem. Concr. Res. 41 (4) (2011) 373–
379.
[32] B. Abu-Jdayil, Rheology of sodium and calcium bentonite–water dispersions:
effect of electrolytes and aging time, Int. J. Miner. Process. 98 (3) (2011) 208–
213.
[33] R. Komatsu, N. Mizukoshi, K. Makida, K. Tsukamoto, In-situ observation of
ettringite crystals, J. Cryst. Growth 311 (3) (2009) 1005–1008.
12 M. Liu et al. / Construction and Building Materials 241 (2020) 118015
[34] S. Luo, M. Liu, L. Yang, J. Chang, Effects of drying techniques on the crystal structure
and morphology of ettringite, Constr. Build. Mater. 195 (2019) 305–311.
[35] P.K. Mehta, Scanning electron micrographic studies of ettringite formation,
Cem. Concr. Res. 6 (2) (1976) 169–182.
[36] K. Ogawa, D.M. Roy, C4A3S hydration, ettringite formation, and its expansion
mechanism: II. Microstructural observation of expansion, Cem. Concr. Res. 12
(1) (1982) 101–109.
[37] T.S. Qureshi, A. Kanellopoulos, A. Al-Tabbaa, Encapsulation of expansive
powder minerals within a concentric glass capsule system for self-healing
concrete, Constr. Build. Mater. 121 (2016) 629–643.
[38] T. Qureshi, A. Kanellopoulos, A. Al-Tabbaa, Autogenous self-healing of cement
with expansive minerals-I: impact in early age crack healing, Constr. Build.
Mater. 192 (2018) 768–784.
 tė, K. Brinkienė, R. Kalpokaitė-Dičkuvienė,
[39] J. Čėsnienė, A. Baltušnikas, I. Lukošiu
Influence of organoclay structural characteristics on properties and hydration
of cement pastes, Constr. Build. Mater. 166 (2018) 59–71.
[40] J. Calabria-Holley, S. Papatzani, B. Naden, J. Mitchels, K. Paine, Tailored
montmorillonite nanoparticles and their behaviour in the alkaline cement
environment, Appl. Clay Sci. 143 (2017) 67–75.
[41] J. Jiang, Z. Lu, J. Li, Y. Xie, K. Luo, Y. Niu, Preparation and properties of
nanopore-rich lightweight cement paste based on swelled bentonite, Constr.
Build. Mater. 199 (2019) 72–81.