J Mater Sci

Composites
COMPOSITES

Effects of nano-SiO2 on the permeability-related

properties of cement-based composites with different
water/cement ratios
Rui Liu2, Huigang Xiao1,2,*, Hui Li1,2, Li Sun3, Zhenyu Pi2, Ghulam Qadir Waqar2, Tao Du2, and Lei Yu2

1
Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, Harbin Institute of Technology, Harbin 150090,
People’s Republic of China
2
Present address: School of Civil Engineering, Harbin Institute of Technology, 73 Huanghe Road, Harbin 150090, Heilongjiang,
People’s Republic of China
3
Department of Mechanical Engineering, University of Houston, Houston, TX 77204, USA

Received: 3 October 2017 ABSTRACT

Accepted: 8 December 2017
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2017
To find the suitable conditions under which nano-SiO2 can exhibit a significant
impermeability enhancement effect and the mechanism underlying this effect,
comparisons between the permeability-related properties of a nano-SiO2-filled
cement paste and those of a reference cement paste composed of different
water/cement (W/C) ratios were carried out in this research. Permeability-
related properties of cement paste, such as the chloride-ion penetration coeffi-
cient (Dnssm), water permeability coefficient (Kp), and initial water sorptivity
coefficient (Si), were tested. Furthermore, Power’s model, mercury intrusion
porosimetry data, and the general effective media theory were also applied to
analyse the evolution mechanism. The results indicate that the effect of nano-
SiO2 on the enhancement of the impermeability becomes more remarkable at a
lower W/C ratio. The decreasing rates of Dnssm, Kp, and Si increase as the W/C
ratio decreases. Furthermore, it can be concluded that the effects of nano-SiO2 on
promoting the hydration, refining the pore structure, narrowing the width of
microcrack and thus enhancing the impermeability of cement paste become
much clearer as the W/C ratio decreases.

Introduction concrete determines the service life of various types

Concrete is the most widely used construction
material in the world, and its properties considerably
affect the performance of concrete structures. As one
of its most crucial properties, the durability of
of infrastructure, and the degradation of concrete and
its structures occur from environmental or loading
impacts [1]. For the durability of concrete, it is
believed that permeability is the most important and
intrinsic characteristic [2], and thus many researchers

Address correspondence to E-mail: xiaohg@hit.edu.cn

https://doi.org/10.1007/s10853-017-1906-8

have been studying the permeability-related aspects
of concrete [3–9].
The permeability of concrete refers to its
microstructural properties, which include the pore
size, interconnection, and distribution, as well as
microcracks [10]. Microvoids in concrete have a
necessity to be refined to provide a voidless concrete
microstructure [11–14], and adding various types of
admixtures and minerals to change the microstruc-
ture of hardened concrete is a feasible method to
obtain a lower permeability [15]. The nano-engi-
neering or nano-modification of cement is a rapidly
growing field. The synthesis and material assembly at
the nanometre scale offer the development possibility
of new cement additives [16–24]. The positive out-
comes achieved by nano-SiO2 in ultra-high-perfor-
mance concrete include strength and durability
[25, 26]. The addition of nano-SiO2 can also reduce
the dosage of cement content by about 20–30% [27].
However, a significant point to consider is whether
nano-SiO2 can play an important role in improving
the properties of concrete under any situation. There
are almost no related reports available at present
revealing under which situation nano-SiO2 will show
a stronger impermeability enhancement effect on
cement paste. Therefore, there is still a need for fur-
ther investigation on the evolution of such effect on
cement paste when applying nano-SiO2.
Previous research has found that, during the pro-
cess of hydration in cement paste with a low W/C
ratio, a C–S–H/CH nano-composite structure is par-
ticularly liable to be formed [28]. Another study
reported that, at lower W/C ratios, the influence of
the recycled aggregate on the mechanical properties
of concrete is superior [29]. Thus, it is expected that at
a low W/C ratio, the addition of nano-SiO2 may have
a special impermeability enhancement effect on
cement paste.
Based on the above review, the aim of the present
research is to explore the effects of nano-SiO2 on the
permeability-related properties of cement-based
composites with different W/C ratios. All nano-SiO2-
filled cement paste (NSCP) and reference cement
paste (CP) specimens used in this research have dif-
ferent W/C ratios. Some permeability-related prop-
erties of cement paste, such as the chloride migration,
water permeability, and initial water sorptivity coef-
ficients, were tested in this research. Meanwhile,
Power’s model, mercury intrusion porosimetry (MIP)
data, and GEM theory were also conducted to
J Mater Sci
analyse the mechanism of the evolution characteristic
of the impermeability enhancement effect of nano-
SiO2.
Experiment programmes
Materials and Procedures
Portland cement PO42.5 and nano-SiO2 were used in
this research. The nano-SiO2 used has a specific sur-
face area of 400 ± 40 m2/g, an average diameter of
20 nm, a purity of 99%, and a bulk density of
B 120 g/L. In addition, W/C ratios of 0.325, 0.35,
0.375, 0.4, 0.425, and 0.45 were used. Moreover, for
the reference cement paste specimens, referred to
here as CP, only Portland cement was used, whereas
in all other research specimens, Portland cement was
replaced by nano-SiO2 at a weight amount of 1.5%,
which is referred to as NSCP. First, in the case of
NSCP, the cement and nano-SiO2 were mixed for
10 min using a cement mixer, and water was then
added into the dry mixture and the mixing continued
for 2 min. Finally, after 24 h of casting, the specimens
were de-moulded. Curing was then applied to the
saturated Ca(OH)2 solution at room temperature for
28 days, and all properties were investigated after the
curing process was finished.
Testing methods
Permeability-related property test methods
Rapid chloride migration test For reinforced concrete
structures, the chloride-ion penetration has been
recognized as a critical intrinsically essential property
of concrete [30]. In this research, the non-steady-state
chloride migration coefficient (Dnssm) was tested
using the chloride-ion diffusion coefficient of a con-
crete and electric flux tester of type CABR–RCMP6
following the ‘non-steady-state chloride migration
test’ (NSSCM) of the European standard (NT
BUILD492) [31]. The test set-up is shown in Fig. 1,
and calculation of Dnssm is given in Eq. (1).
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
0:0239ð273þTÞL ð273 þ TÞLxd
Dnssm ¼ xd  0:0238 :
ðU  2Þt U2
ð1Þ
Here, Dnssm is the coefficient of non-steady-state
migration (10-12 m2/s), U is the absolute applied
J Mater Sci

Figure 1 Chloride-ion diffusion coefficient measurement set-up.

1-anode plate; 2-anodic solution (0.3 mol/L NaOH); 3-test Figure 2 Schematic arrangement of WPT set-up used in this
specimen; 4-the cathode solution (10% NaCl); 5-DC stabilized research. 1-cell 1, 2-PVC tube, 3-pan, 4-plastic sheet, 5-glass
power supply; 6-organic silicone rubber sleeve; 7-strap; 8-minus cement, 6-specimen, 7-cell 2.
plate; 9-cradle head; 10-the cathode test slot; 11-support.
The test set-up shown in Fig. 2 is a simplified and
voltage value (V), T is average value of the initial and improved version based on previous studies [34–37].
final temperatures in the anolyte solution (°C), L is Before the test programme, the mass of water in cell
the specimen thickness (mm), xd is the average pen- 1, as shown in Fig. 2, was measured as m0. After the
etration depth over the central zone as revealed by test was conducted for time t, the mass of water in
colouring of AgCl (mm), and t is the test duration (h). cell 1 was measured as m1, and H1 could then be
obtained through Eq. (4). Combining Eqs. (3) and (4),
Water permeability test Water is the main agent Kp in Eq. (5) is obtained, where q is the density of
responsible for the structural degradation of concrete water.
[32], and thus the water permeability of concrete is m0  m1
H1 ¼ H0  DH ¼ H0  ; ð4Þ
very important in regard to concrete durability [33]. qA0
An apparatus for a water permeability test (WPT) A0 L H0
was described in [34–37], and the water permeability KP ¼ ln  : ð5Þ
At H0  m0 m0 1
coefficient (Kp) was obtained using Darcy’s law based qA
on the unit time of the water flow, as expressed in
Eq. (2); the value of Kp can thus be calculated through
Water sorptivity test The absorption capacity, ‘sorp-
Eq. (3) according to [34–37].
tivity’, is an easily measurable material property
Qf A0 dH HA characterizing the tendency of water absorption of a
¼ ¼ Kp ; ð2Þ
dt dt L porous material based on its capillary action [38]. The
A0 L H0 water sorptivity test (WST) conducted in this study
Kp ¼ ln : ð3Þ
At H1 was based on the ASTM: C1585-13 standard [39]. The
coefficient of initial absorption (Si) was measured
Here, Qf is the total water flow, Qf/dt is the flow rate,
using Eqs. (6) and (7).
Kp is the permeability coefficient, A is the cross-sec-
mt
tional area of the concrete, A0 is the area of the pip- I¼ ; ð6Þ
ette, l is the thickness of the sample, t is the time ad
between two successive readings, and H0 and H1 are Ii ¼ Si t0:5 þ b: ð7Þ
the water head at the start and end of the test,
Here, the absorption is denoted by I, the change in
respectively.
specimen mass in grams is indicated as mt at time t,

the exposed area is shown by a of the measured
specimen in mm2, the density of water is termed
d and is measured in g/mm3, and the initial
absorption coefficient in mm/s1/2 is Si.
In addition to the above permeability-related
properties, the mechanical properties of the speci-
mens, including the three-point bending strength
(TBS) and compressive strength (CS), were also tested
according to the Chinese standard GB/T 17671-1999
[40].
Pore structure measurement
Mercury intrusion porosimetry method The MIP tech-
nique was applied to test the pore structure of the
specimens in this research owing to its wide mea-
suring range of the pore diameter, quickness, and
simplicity [41, 42]. The theory, method, and prepa-
ration of the samples for the MIP testing follow those
of previous studies [41, 43, 44]. The testing was con-
ducted using an Autopore IV 9500 instrument, with
mercury of about 13.5335 g/mL in density, a surface
tension of 485 dynes/cm, and a contact angle of 130°.
At most, 33000 psi of pressure was applied for the
measurement, which indicates that the minimum
pore diameter that can be considered approaches
5.65 nm.
Results and discussion
Permeability-related properties
Here, Dnssm, Kp, and Si are permeability-related
properties that can be used to efficiently evaluate the
ability of a substance transmission in cement paste,
and a low value of these properties indicates that the
liquid transfer efficiency in the paste is low and the
penetration resistance is strong. These permeability-
related properties along with three-point bending
strength and compressive strength were tested
according to the method described in ‘‘Permeability-
related property test methods’’ section; the results of
which are shown in Table 1.
It can be clearly seen from Table 1 that the values
of Dnssm, Kp, and Si for both CP and NSCP decreased
as the W/C ratio was reduced and that the penetra-
tion resistance of NSCP is stronger than that of CP at
the same W/C ratio, proving that the addition of
nano-SiO2 improved the impermeability of the
J Mater Sci
cement paste. The change rate (CR/%) calculated
using Eq. (8) was then used in this research to
describe how much nano-SiO2 can improve the
properties of cement paste. The results of the CR are
provided in Fig. 3.
jPNSCP  PCP j
CR ¼  100 ð8Þ
PCP
Here, PNSCP indicates the property value of NSCP,
whereas PCP indicates the property value of CP.
The dashed lines in Fig. 3 show that the decreasing
rates of Dnssm, Kp, and Si increased as the W/C ratio
decreased, illustrating that as the W/C ratio is
reduced, the effect of nano-SiO2 on improving the
penetration resistance of the cement paste becomes
more significant.
The values of TBS and CS increase as the W/C ratio
decreases, as shown in Table 1. In addition, these two
properties for NSCP are higher than those for CP
with same W/C ratio, demonstrating that the addi-
tion of nano-SiO2 improves the mechanical properties
of cement paste. However, a similar trend in the
change rate shown in terms of the permeability-re-
lated properties did not appear in this study.
Analysis of hydration
The degree of hydration and the resulting hydration
products can directly lead to the formation of a
microstructure in CP and NSCP, and thereby influ-
ence the permeability of the cement paste. In this
study, Power’s model [45, 46] was used to analyse the
hydration of CP and NSCP such that the evolution
mechanism of the impermeability enhancement effect
of nano-SiO2 on cement paste can be better known.
The degree of hydration (a), the volume fraction of
the hydration products (Vhyd.), and the volume frac-
tion of C–S–H in the solid phase (UC–S–H) are all
important parameters to describe the hydration of
cement, and their values can be obtained using
Eqs. (9)–(12) [45, 46], respectively; the calculated
results are as shown in Table 2.
ð1  UÞðW=CÞ  0:32U
a¼ ; ð9Þ
0:36
0:68a
Vhyd: ¼ ; ð10Þ
ðW/C) + 0:32
VCSH
UCSH ¼ ; ð11Þ
Vunhyd: þ VCH þ VCSH
J Mater Sci

Table 1 Permeability-related properties

Samples W/C Dnssm/1E-12 (m2/s) Kp/1E-10 (m/s) Si/1E-2 (mm/s0.5) TBS (MPa) CS (MPa)

NSCP 0.325 4.96 2.24 0.12 11.65 85.85

0.35 6.39 2.70 0.17 9.92 75.49
0.375 8.51 5.14 0.18 8.81 72.11
0.4 9.89 5.96 0.30 8.63 65.31
0.425 10.58 6.56 0.36 8.47 63.12
0.45 13.65 8.94 0.42 7.02 58.40
CP 0.325 9.34 16.59 0.28 8.83 77.98
0.35 10.25 18.44 0.39 8.91 70.26
0.375 10.52 19.35 0.39 8.07 66.18
0.4 12.10 19.56 0.42 7.69 64.25
0.425 12.49 19.71 0.45 6.04 55.31
0.45 16.02 21.45 0.50 5.93 46.88

information into Eq. (10), the volume fraction of C–S–

90
■ K p fitting line of K p H (VC–S–H) can be obtained [45, 46]. In addition,
▲S fitting line of S i
● Dnssm
i
fitting line of Dnssm Vunhyd. is the volume fraction of the un-hydrated
75 cement particles.
It can be seen from Table 2 that a, Vhyd., and UC–S–H
Change rate / %

60
of both CP and NSCP increased as the W/C ratio
increased. Moreover, under the same W/C ratio, the
45
values of a, Vhyd., and UC–S–H of NSCP are higher
30
than those of CP, which reveals that the hydration
taking place in NSCP is more sufficient than that in
15 CP, leading to more hydration products and C–S–H
generation in NSCP. Furthermore, it can be seen from
0.450 0.425 0.400 0.375 0.350 0.325 the dashed lines in Fig. 4 that the increasing rates of
W/C ratio a, Vhyd., and UC–S–H from CP to NSCP, as calculated
using Eq. (8), increased as the W/C ratio decreased,
Figure 3 Change rate of permeability-related properties versus
water/binder ratio. meaning that nano-SiO2 plays an increasingly sig-
nificant role in promoting the hydration of cement
0:32ð1  aÞ paste when the W/C ratio is lower.
Vunhyd: ¼ : ð12Þ Thermogravimetric analysis (TGA) curves tested
ðW/C) + 0:32
by STA449F3-type thermal analyser can be found in
Here, ‘U’ is the capillary porosity of cement paste, Fig. 5. It can be seen from Fig. 5 that there is an
W/C is the water–cement ratio, and VC–S–H/ obvious degradation stage around 443–468 °C,
VCH = 1.66:0.63 is the chosen value for ordinary showing the dehydration phase of calcium hydrox-
portland cement (OPC) paste [47]; substituting this ide, which can also be observed from similar studies

Table 2 Hydration-related
data based on Power’s model Samples W/C U (mL/g) a (%) Vhyd (%) UC–S–H (%) lc (nm)

NSCP 0.325 0.0671 0.7826 0.8251 0.6411 26.3173

0.375 0.0738 0.8992 0.8798 0.6886 32.3964
0.425 0.1027 0.9681 0.8836 0.7138 40.3220
CP 0.325 0.0768 0.7652 0.8067 0.6334 32.3960
0.375 0.0815 0.8844 0.8653 0.6829 32.4027
0.425 0.1090 0.9550 0.8717 0.7092 40.3191
 J Mater Sci

2.4 Pore structure characteristics

■ Φcsh fitting line of Φcsh
●α fitting line of α
The capillary porosity (U) and critical pore diameter
▲V fitting line of Vhyd
hyd
2.0 (lc) of both CP and NSCP can be seen from the MIP
results in Fig. 6, the values of which, shown in
Change rate /%

1.6 Table 2, can be obtained based on a previous method

[46]. According to the MIP test results shown in
Fig. 7, four types of pores with sizes of \ 20, 20–100,
1.2
100–200, and[ 200 nm, respectively, occupy the total
porosity, ranging from 28.0–39.2%, 50.0–56.3%,
0.8 0.6–1.1%, to 8.8–20.3%. Moreover, because pores of
\ 20 nm in size are harmless [32], the pores of
0.425 0.400 0.375 0.350 0.325 20–100 nm in size mostly determine the permeability
W/Cratio of CP and NSCP.
Figure 4 Change rate of hydration products-related parameter At the same W/C ratio, the degree of hydration of
versus water/binder ratio. NSCP is higher than that of CP, meaning that there is
more water consumed for hydration and less water
-9 CP-W/C=0.325 left to evaporate in NSCP than in CP, which leads to
CP-W/C=0.375
CP-W/C=0.375
-10 NSCP-W/C=0.325
NSCP-W/C=0.375
0.30 CP-W/C=0.325
NSCP-W/C=0.425
CP-W/C=0.375
Log differential intrusion/ mL/g

-11 CP-W/C=0.425
0.25
NSCP-W/C=0.325
TG/ %

NSCP-W/C=0.375
-12 0.20 NSCP-W/C=0.425

-13 0.15

-14 0.10

0.05
440 450 460 470 480 490
T/ 0.00

10 100 1000 10000

Figure 5 Thermogravimetric analysis curves.
Pore size diameter/nm
(a)
in some literatures [48, 49]. Moreover, the lost weight
percent of NSCP with W/C ratio of 0.325, 0.375, and
Cumulative pore int./ext. volume /(mL/g)

0.14 CP-W/C=0.325
0.425 is 1.20, 1.45, and 1.83%, respectively, which is CP-W/C=0.375
smaller than that of CP (2.16, 2.17, and 2.40%), 0.12
CP-W/C=0.425
NSCP-W/C=0.325
demonstrating that there is less calcium hydroxide NSCP-W/C=0.375
0.10 NSCP-W/C=0.425
and more C–S–H gel in NSCP due to the reaction of
nano-SiO2 and Ca(OH)2. Furthermore, the decreasing 0.08
rates from the lost weight percent of CP to that of
0.06
NSCP calculated using Eq. (8) are 23.8, 32.9, and
44.4% severally as W/C ratio becomes lower. Con- 0.04
sequently, it can be concluded that, as W/C ratio
0.02
becomes lower, nano-SiO2 can consume more
Ca(OH)2 to produce more resultants such as C–S–H 0.00
10 100 1000 10000
gel and obviously improve the impermeability of
Pore size diameter/nm
cement paste. (b)

Figure 6 MIP test results of specimens.

J Mater Sci

0.07 CP-W/C=0.425 ■ CP
NSCP-W/C=0.425 0.11 ● NSCP
0.06 fitting line of CP
CP-W/C=0.375
fitting line of NSCP
NSCP-W/C=0.375 0.10 W/B=0.325
0.05
Porosity/ (mL/g)

CP-W/C=0.325 W/B=0.375

Φ /(mL/g)
NSCP-W/C=0.325 0.09 W/B=0.425
0.04

0.08
0.03

0.07
0.02

0.01 0.06

0.00
20 20~100 100~200 200 0.75 0.80 0.85 0.90 0.95
Pore size/nm α
(a)
Figure 7 Pore size distribution voids.
0.070 ■ CP
● NSCP
fitting line of CP
0.065
the notion that the capillary porosity and the porosity fitting line of NSCP
W/B=0.325
of 20–100-nm-sized pores (U20–100 nm) are negatively Φ20~100nm / (mL/g) 0.060 W/B=0.375
related to the degree of hydration, as indicated by the W/B=0.425

arrow lines in Fig. 8a, b. Therefore, UNSCP and 0.055

U20–100 nm, NSCP are lower than UCP and U20–100 nm, CP, 0.050
respectively, under the same W/C ratio, as described
in Table 2. Furthermore, the decreasing rate from UCP 0.045

to UNSCP and from U20–100 nm, CP to U20–100 nm, NSCP,

0.040
respectively, as calculated using Eq. (8), increased
0.75 0.80 0.85 0.90 0.95
when the W/C ratio was reduced, as shown in the
α
dashed lines in Fig. 8. It has been generally (b)
acknowledged that smaller critical pore diameter
results in finer pore structure [46]. The value of lc has 42 ■ CP
a negative correlation with a when the W/C ratio is
40
● NSCP
fitting line of CP
0.325, whereas lc remains nearly unchanged as a is fitting line of NSCP
38
increased at W/C ratios of 0.375 and 0.425, as indi- W/B=0.325
36 W/B=0.375
cated by the arrow lines in Fig. 8c. This indicates that, W/B=0.425
lc/nm

at a low W/C ratio (0.325), lc of NSCP is clearly 34

smaller than that of CP, as described in Table 2, and 32

thus the decreasing rate of lc from CP to NSCP, as 30
calculated through Eq. (8), clearly increases at a low 28
W/C ratio, as shown with the dashed curve in Fig. 9.
26
It can be seen from the dashed lines in Fig. 8 that U,
U20–100 nm, and lc of both CP and NSCP have positive 0.75 0.80 0.85
α
0.90 0.95

correlations with a, which indicates that when the (c)

degree of hydration and the amount of water used for
hydration increase, the amount of water evaporated
from both CP and NSCP also increases. Therefore, as
the total amount of water or the W/C ratio increases,
U, U20–100 nm, and lc of both CP and NSCP increase, as
the data in Table 2 and Fig. 7 show.
The above analysis indicates that the hydration
positively influences the formation of the pore
Figure 8 Relationship between pore structure parameter and
hydration degree. a The relationship between U and a; b the
relationship between 20- and 100-nm-sized pore volume and a;
c the relationship between lc and a.
structure in cement paste and makes the pore struc-
ture of NSCP more optimal and refined than that of
CP. Furthermore, the effect of nano-SiO2 on refining
 J Mater Sci

and 3.08–3.52 in NSCP with W/C ratio of 0.325, 0.375,

20 ■ lc fitting curve of lc and 0.425. Additionally, due to the high reactivity of
●Φ fitting line of Φ
▲Φ fitting line of Φ20~100nm nanoparticles [50], nano-SiO2 can react with Ca(OH)2
20~100nm
15 crystals to produce C–S–H gel [51, 52]. As a result, it
can be concluded that in NSCP, those tiny products,
Change rate /%

10 generated after the reaction between nano-SiO2 and

Ca(OH)2, narrowed the width of microcrack, espe-
cially in cement paste with low W/C ratio, and were
5
able to enhance the impermeability of cement paste
obviously.
0

Effects of pore structure on permeability

0.425 0.400 0.375 0.350 0.325 based on GEM theory
W/C ratio
The GEM theory was proposed by Mclachlan et al.
Figure 9 Change rate of pore structure parameter versus water/ [53–56] and is applicable to the calculation of the
binder ratio. overall cement permeability. In this model, cement is
regarded as a type of two-phase composite material
the pore structure of cement paste is much more
[46]. Of these two phases, one is a capillary pore
conspicuous when the W/C ratio is lower.
phase with high penetrability and the other is a
hyposmosis phase including C–S–H gel, CH, and un-
Analysis of characteristic of microstructure
hydrated cement particles.
In cement paste, the microcracks can make significant In this study, the penetrability of a high-perme-
influence on the permeability of cement paste. Merlin ability phase (kh) and all of the cement (k) can be
Compact-type field emission scanning electron calculated using the MIP test results as well as
microscope was used to observe the microstructure of Eqs. (13)–(16) [46], respectively. The calculated
CP and NSCP, and the SEM micrographs are shown results are shown in Table 4.
in Fig. 10. On the one hand, it can be seen from 1=t 1=t
ð1  UÞðkl  k1=t Þ Uðkh  k1=t Þ
Fig. 10a, c, and e that W/C ratio becomes lower and 1=t
þ 1=t
¼ 0; ð13Þ
kl þ Ak1=t kh þ Ak1=t
the microcrack width turns smaller in CP. In addi-
tion, on the edge and around of the microcrack, there 1 2
kh ¼ l ð1:8Þð1  Uc Þ2 ; ð14Þ
is nearly no attached material, causing that some 226 c
 
external materials such as fluid can easily seep into 1  UCSH 2
the inside of cement paste through these microcracks. kl ¼ kCSH 1  ; ð15Þ
1  U0c
On the other hand, Fig. 10b, d, and f obviously shows
1  Uc
that there are many tiny products germinated on the A¼ : ð16Þ
surface of crack edge and its ground in NSCP. Fur- Uc
thermore, as W/C ratio becomes lower and the Here, Uc is the critical capillary porosity, which is
microcrack width narrows down in NSCP, these tiny equal to 0.18 [46]; kl describes the low-permeability
products are able to gradually cover (Fig. 10d) and phase; Uc0 describes the critical volume fraction of C–
even infill (Fig. 10f) the microcrack. Therefore, these S–H, which was to be chosen to be 0.17 [57]; and
tiny products in NSCP can effectively improve the kC–S–H, the permeability of the C–S–H gel, is equal to
dense degree of cement paste, eventually decreasing 7 9 10-23 m2 [58].
its permeability. It can be seen from the dashed lines in Fig. 11a and
The main components of the tiny products were b that kh has a positive correlation with lc and U; in
also tested, and the EDS results are shown in Table 3. addition, k is positively related to lc and U, as shown
According to Table 3, we can see that these tiny in Fig. 11c and d, respectively. Therefore, both k and
products are mainly composed of Ca, Si, and O, and kh increase as the W/C ratio increases, and k and kh of
the n(Ca)/n(Si) ratios (C/S) are 2.06–2.91, 2.16–3.33, NSCP are lower than that of CP under the same W/C
J Mater Sci

Figure 10 SEM micrograph of CP and NSCP. a CP with W/C ratio of 0.425; b NSCP with W/C ratio of 0.425. c CP with W/C ratio of
0.375; d NSCP with W/C ratio of 0.375. e CP with W/C ratio of 0.325; f NSCP with W/C ratio of 0.325.

ratio, as the data in Table 4 indicate. Moreover, the Conclusions

decreasing rate of k and kh from CP to NSCP calcu-
lated using Eq. (8) increases as W/C ratio decreases,
as the dashed lines in Fig. 12 show.
The above analysis proves that the pore structure
characteristics positively influence the permeability
of cement paste and make the impermeability of
NSCP stronger than that of CP. Furthermore,
impermeability enhancement effect of nano-SiO2 is
much more conspicuous, particularly at a lower W/C
ratio.
1. The impermeability enhancement effect of nano-
SiO2 on cement paste becomes more noteworthy
as the W/C ratio is decreased. The decreasing
rate of the chloride migration, water permeabil-
ity, and initial water absorption coefficients
increases as the W/C ratio decreases.
2. Nano-SiO2 plays an increasingly significant role
in promoting the hydration of cement paste as the
W/C ratio is reduced. From CP to NSCP, the
increasing rates of the degree of hydration,
 J Mater Sci

Figure 11 Relationship between permeability based on the GEM c 9.00E-018 ■ CP

theory and pore structure parameter. a The relationship between kh ● NSCP
fitting line of CP
and lc; b the relationship between kh and U; c the relationship 8.00E-018
fitting line of NSCP
between k and lc; d the relationship between k and U.
7.00E-018

k h / m2
6.00E-018

volume fraction of the hydration products, and 5.00E-018

volume fraction of C–S–H in a solid phase all
4.00E-018
increase as the W/C ratio decreases.
3. The hydration positively influences the formation 3.00E-018
26 28 30 32 34 36 38 40
of a pore structure in cement paste, and the pore lc/nm
structure characteristics positively influence the (a)
cement paste permeability. The resulting effect of
nano-SiO2 on refining the pore structure and
9.00E-018 ■ CP
● NSCP
enhancing the impermeability of cement paste is 8.00E-018 fitting line of CP
fitting line of NSCP
much more conspicuous, particularly when the
7.00E-018
W/C ratio is lower.

k h / m2
4. Some tiny products, generated after the reaction 6.00E-018

between nano-SiO2 and Ca(OH)2, narrowed the 5.00E-018

width of microcrack, especially in cement paste
with low W/C ratio. 4.00E-018

5. The evolution of the impermeability enhance- 3.00E-018

0.07 0.08 0.09 0.10 0.11
ment effect of nano-SiO2 on cement paste can
Φ/(mL/g)
provide a theoretical foundation for the effective
(b)
use of nano-SiO2 and improving the anti-perme-
ability of cement-based composites with a low
1.40E-022 ■ CP
● NSCP
fitting line of CP
1.20E-022 fitting line of NSCP
Table 3 EDS results of tiny products in NSCP

Test zone Wt% Atomic percent C/S

k / m2

1.00E-022

O Si Ca O Si Ca
8.00E-023

1 56.61 8.05 35.34 75.18 6.09 18.74 3.08

6.00E-023
2 50.06 8.29 41.65 70.10 6.62 23.28 3.52
3 51.29 8.82 39.89 71.00 6.96 22.04 3.17
26 28 30 32 34 36 38 40
4 45.07 9.55 45.38 65.68 7.92 26.40 3.33
lc/nm
5 57.64 10.39 31.97 75.52 7.75 16.72 2.16
(c)
6 51.94 11.17 36.89 71.12 8.71 20.16 2.31
7 46.28 10.43 43.29 66.59 8.55 24.86 2.91 1.40E-022
■ CP
8 52.20 12.13 35.68 71.16 9.42 19.42 2.06 ● NSCP
fitting line of CP
1.20E-022 fitting line of NSCP
k / m2

Table 4 Permeability based on GEM theory 1.00E-022

2 2
Samples W/C Kh (m ) K (m )
8.00E-023

NSCP 0.325 3.709E-18 5.543E-23

0.375 5.621E-18 7.507E-23 6.00E-023
0.425 8.707E-18 1.279E-22
CP 0.325 5.620E-18 6.384E-23 0.07 0.08 0.09 0.10 0.11
0.375 5.623E-18 8.174E-23 Φ/(mL/g)
0.425 8.706E-18 1.377E-22 (d)
J Mater Sci

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