Construction and Building Materials 252 (2020) 119037

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Construction and Building Materials

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

Preparation and properties of nanosilica-doped polycarboxylate

superplasticizer
Chunrong Ren, Li Hou, Jun Li ⇑, Zhongyuan Lu ⇑, Yunhui Niu
National Engineering Technology Center for Insulation Materials, State Key Laboratory of Environment-friendly Energy Materials, School of Materials Science and
Engineering, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Nanosilica-doped polycarboxylate
superplasticizer (NS/PCE) was
prepared.

NS/PCE has the increased adsorption
capacity and better dispersion for
cement.

NS/PCE can effectively reduce
orientation coefficient of Ca(OH)2.

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

Article history: Combination of nanoparticles and polycarboxylate superplasticizers (PCE) is expected to synchronously
Received 5 November 2019 improve the workability, mechanical properties and durability of the mortars and concretes. In this study,
Received in revised form 16 March 2020 nanosilica (NS) has been introduced and grafted onto PCE molecular chains through radical polymeriza-
Accepted 5 April 2020
tion. Nanosilica-doped polycarboxylate superplasticizer (NS/PCE) was thus obtained and used as the
modified water reducer in cement pastes and mortars. The effect of NS/PCE on adsorption, dispersion
and mechanical properties of cement pastes or mortars has also been investigated. Results showed that
Keywords:
PCE had been chemically bonded to anchor onto the surface of NS by Si-O-. NS was uniformly dispersed in
Polycarboxylate superplasticizer
Nanosilica
PCE due to the steric resistance and electrostatic repulsive force. The as-obtained NS/PCE had better dis-
Dispersion persion and enhanced adsorption performance compared to that of the undoped PCE. NS/PCE can effec-
Adsorption tively reduce the amount and orientation coefficient of Ca(OH)2 crystals in cement-based materials,
Mechanical properties which is beneficial to the microstructure refinement and the mechanical properties improvement of
cement matrix.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction nanomaterials, such as nano-SiO2 [1–3], nano-Al2O3 [4], nano-

Nanomaterials are expected to play much more important
roles in construction and building materials. Various types of
⇑ Corresponding authors.
E-mail addresses: lijun@swust.edu.cn (J. Li), luy@swust.edu.cn (Z. Lu).
Fe2O3 [5], nano-CaCO3 [6], nano-TiO2 [7], nano-clay [8], C-S-H
seeds [9], carbon nanotubes/fibers [10], graphene/graphene oxide
[11], etc., have been researched to improve the mechanical
properties, durability and some functions of cement composites
[12]. As known, nanoscale effect of nanoparticles in cement-
based materials is strongly relied on its dispersion. However, it is

https://doi.org/10.1016/j.conbuildmat.2020.119037
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 C. Ren et al. / Construction and Building Materials 252 (2020) 119037
also a challenge for the even dispersion of nanoparticles in cement
pastes, mortars and concretes without pretreatment.
Ultrasonic dispersion and surfactants assisted dispersion of
nanoparticles into water solutions were the generally adopted
ways before that the nanoparticles were added into cement-
based mixtures [13–15]. Ultrasonic dispersion is much more com-
plicated and difficult to be applied in the actual project. Another
way to improve the nanoparticles dispersion in cement-based mix-
tures is to modify it by surfactants. Collodetti et al. reported that
the modification of NS by using sodium dodecyl sulfate, c-amino
propyltriethoxysilane and methacryloxyethyltrimethyl ammo-
nium chloride, and the enhanced hydrophobicity and inhibited
agglomeration of nanoparticles were observed [16]. Unfortunately,
majority of modifiers for nanoparticles modification are incompat-
ible with cement, which would degrade the performances of
cement-based materials. Polycarboxylate superplasticizer (PCE) is
a kind of surfactants widely used in modern cement-based materi-
als, it can also be used as an effective dispersant for nanoparticles
[17]. It is proved that the workability, mechanical properties and
durability of the cement pastes, mortars and concretes containing
both nanoparticles and PCE would all be improved due to the even
dispersion of nanoparticles by PCE. However, PCE would be firstly
adsorbed by nanoparticles with larger specific surface area, which
reduced the dispersion effect of PCE for cement particles and
greatly increase the PCE dosage in fresh cement-based slurry.
Researchers reported the surface modification of nanoparticles by
PCE before used, and the so-called NS@PCE core–shell nanoparti-
cles were obtained [18]. It seems that NS@PCE had better disper-
sion in cement paste while its pozzolanic activity was also
preserved. Gu et al. synthesized NS@PCE nanoparticles with
core–shell structure by grafting PCE containing vinyl triethoxysi-
lane on the surface of NS, and observed that most of NS reacted
with Ca(OH)2 (CH) to form C-S-H gels due to the agglomeration
reduction [19]. Huang et al. reported that the surface modification
of NS by using PCE containing c-(methacryloyloxy)propyltrime
thoxysilane under microwave heating and found that cement
pastes mixed with modified NS has higher fluidity than that of
the pastes mixing with unmodified NS [20]. It is found that NS
modified by PCE could be well dispersed in cement paste, mortar
or concrete, however, PCE should also be added again as the water
reducers when commercial mortars or concretes are produced by
using NS modified by PCE in this case. From the engineering point
of view, NS modified by PCE itself should be also used as the water
reducer when it was applied. Researches mentioned above indi-
cated that Si-OH groups of NS could be grafted onto molecular
chains of PCE, that is, it is possible to obtain a new-type functional
PCE through the modification of PCE by NS.
Presumably, PCE modified/doped by NS has the synergistic
effect of water reduction, mechanical properties enhancement
and durability improvement for cement composites. In this study,
NS/PCE has been synthesized and characterized. The effect of NS/
PCE on properties of fresh or hardened cement pastes and mortars
has also been studied.
2. Experimental
2.1. Raw materials
Acrylic acid (AA), mercaptopropionic acid (MPA), hydrogen peroxide solution
(H2O2, 27.5%), ascorbic acid (VC) used in this study were all analytical reagents
and without further purification. Isoprenyloxy polyethylene glycol (TPEG,
Mw = 2400) was industrial grade. NS suspension with mean particle size of 12 nm
and solid content of 30% by mass was supplied by DezhouJinghuo Technique Glass
Co., Ltd. (Dezhou, Shandong Province, China). Ordinary Portland cement PO 42.5R
was produced by Lafarge Shuangma Cement Plant (Jiangyou, Sichuan Province,
China), chemical composition of cement is listed in Table 1. Standard sands were
produced by ISO Standard Sand Co., Ltd (Xiamen, Fujian Province, China) according
to Chinese standard GB/T17671-2005 [21], which were composed of coarse sands
(1–2 mm), medium sands (0.5–1 mm) and fine sands (0.08–0.5 mm) and each of
the three sands accounted for a third by mass.
2.2. Preparation
2.2.1. Preparation of NS/PCE
Solution A was obtained by mixing 6.9 g AA and distilled water. Solution B was
obtained by mixing 0.236 g MPA, 0.113 g VC and distilled water. 70 g TPEG and dis-
tilled water were gradually heated to 30 °C, stirred to dissolve and then added H2O2
solution with 0.14% mass fraction of TPEG to form solution C. Solution A and B were
slowly added into solution C at 30 °C by peristaltic pumps, the dripping time was
controlled at 2 h and 2.5 h, respectively. pH of the mixed solution was controlled
at 8 by adding proper content of NaOH solution, the obtained solution with solid
content of 40% was the PCE. NS suspension was dropwise added to the above pre-
pared PCE within 2 h by peristaltic pumps. The reaction was further incubated for
1.5 h and then cooled to the room temperature, NS/PCE1, NS/PCE2, NS/PCE3 and NS/
PCE4 with NS content of 5%, 10%, 20% and 30% of TPEG, respectively, were finally
obtained. The above reaction products were filtered by semi-permeable membrane
(MD44-7) before tested.
2.2.2. Preparation of cement pastes and mortars
Cement (500 g), PCE or NS/PCE (0.15% weight of cement) and water (water to
cement ratio (w/c) was 0.29) were mixed and blended to prepare cement pastes
according to Chinese standard GB/T 8077-2012 [22]. Cement mortars were pre-
pared by mixing cement, water, sand and PCE (or NS/PCE) according to Chinese
standard GB/T 17671-2005 [21]. Sand to cement ratio was controlled at 3 by mass.
The content of PCE (or NS/PCE) in mortars is 0.3% of cement by mass. As shown in
Table 2, required water in preparation of mortars could be obtained when the mor-
tar fluidity was controlled at 180 ± 5 mm. Thus, the water-reducing rate of PCE (or
NS/PCE) could be calculated based on the water requirement at the same mortar
fluidity (Table 2). The mix design of mortars was listed in Table 2.
2.3. Test methods
Relative molecular mass (Mn denotes number-average molar mass, Mw denotes
weight-average molar mass) and polydispersity index (PDI, PDI = Mw/Mn) were
determined by gel permeation chromatography (GPC, Agilent Technologies, Amer-
ica). The mobile phase was 0.1 mol/L NaNO3 solution at a flow rate of 1 mL/min. The
polymer was dissolved in water at a concentration of 1 mg/mL and then filtered
through a 0.22 lm microporous membrane. Subsequently, the sample was tested
at a flow rate of 1 mL/min at room temperature.
Fourier infrared (FT-IR) spectroscopic analysis was tested on an IS5 Fourier
infrared spectrum analyzer (Thermo Scientific, America).
Grafting content of NS in NS/PCE was measured by using a simultaneous ther-
mal analyzer (STA8000, PerkinElmer, America) in the temperature range from 30 °C
to 800 °C at a constant heating rate of 10 °C/min in N2 atmosphere. Before test, PCE
and NS/PCE were centrifuged (10,000 r/min, 10 mins) to remove impurities.
Zeta potential of cement paste was measured by a zeta potential and particle
size analyzer (zetaPALS, Brookhaven Instruments, America) at 25 °C. 0.25 g cement
and 100 mL NS/PCE solutions were stirred for 5 min and then left standing for
10 min. Then the supernatant was quickly introduced into a sample cell for the zeta
potential test. Each sample was tested for three times, and the average value was
taken as the final result.
Adsorption amounts of superplasticizer on cement particles were examined by
the ultraviolet spectrophotometer (UV2600, Shimadzu, Japan). The wavelength of
superplasticizer is 198 nm. Cement pastes were prepared by 10 g cement, 50 g
water, and predetermined amount of superplasticizer solution with a concentration
of 0.1–1.6%. The specific test steps referred to the literature [23].
X-ray diffraction (XRD) test was performed on an X-ray diffractometer
(DMAX1400, Rigaku, Japan) in the 2-theta range of 5-75°. Thermo gravimetric
(TG) experiments were conducted on a simultaneous thermal analyzer (STA8000,
PerkinElmer, America) in the temperature range from 30 °C to 1000 °C at a constant
heating rate of 20 °C/min in N2 atmosphere. Hardened cement pastes were
immersed in anhydrous ethanol for 24 h to terminate the hydration, then the sam-
ples were dried in a vacuum at 40 °C to constant weight before XRD and TG test.
Morphology of NS and NS/PCE was observed by transmission electron micro-
scopy (TEM, Libra200, Carl Zeiss, Germany). NS or NS/PCE was firstly diluted into
deionized water, a drop of diluted solution was added onto a copper mesh for
TEM test. The microstructure of cement hydration products was observed by scan-
ning electron microscopy (SEM, TM-4000, Hitachi Limited, Japan). A 5  5  2 mm3
hardened paste was cut and then immersed in anhydrous ethanol for 24 h to stop
hydration, then dried in a vacuum at 40 °C to constant weight for SEM test.
Fluidity of cement paste was carried out in accordance with Chinese standard
GB/T 8077-2012 [22]. Compressive and flexural strength of hardened cement mor-
tars were tested according to Chinese standard GB/T 17671-2005 [21].
 C. Ren et al. / Construction and Building Materials 252 (2020) 119037 3

Table 1
Chemical composition of cement (wt%).

CaO SiO2 SO3 Al2O3 Fe2O3 MgO K2O TiO2 P2O5 Na2O Loss
65.87 18.95 4.88 4.53 3.22 0.91 0.83 0.31 0.25 0.58 0.52

Table 2
Mix design of mortars and the water-reducing rate of NS/PCE.

Sample Cement (g) Sand (g) Water reducer (g) Water (g) Fluidity (mm) Water-reducing rate (%) w/c
Blank 450 1350 0 200.00 183 0 0.44
PCE 1.35 150.68 185 30.23 0.34
NS/PCE1 1.35 143.60 184 33.21 0.32
NS/PCE2 1.35 147.55 182 31.37 0.33
NS/PCE3 1.35 154.92 185 27.95 0.34
NS/PCE4 1.35 159.65 185 25.74 0.36

3. Results and discussion
3.1. Characterization of NS/PCE
FT-IR spectras of NS, NS/PCE3 and PCE are shown in Fig. 1. It is
pointed out that FT-IR spectra of NS/PCE3 has been chosen as the
representative result in this study due to the spectra similarity
for NS/PCE system. A new absorption peak at about 1730 cm1
appears in FT-IR spectra of NS/PCE3 compared to that of NS and
PCE, which can be attributed to the symmetric stretching vibration
of ester carbonyl group [24,25]. The active hydroxyl group on NS is
esterified with the carboxy group of PCE, which indicates that NS
particles have been grafted onto the PCE molecules. That is, PCE
is chemically bonded by Si-O to anchor onto the surface of NS.
NS/PCE solutions after 30 mins and 3 days placing are presented
in Fig. 2. NS/PCE1, NS/PCE2 and NS/PCE3 solutions were all stable
and relatively transparent after 30 mins or 3 days placing. NS/
PCE4 seemed to be the white emulsion after 30 mins placing and
would be layered after 3 days placing. Micellar transition of NS
occurred under induction of PCE when too many NSs were intro-
duced, which would result in the formation of larger colloidal par-
ticles [26]. Hence, larger colloidal particles deposited to the bottom
of tubes in NS/PCE4.
TEM images of NS and NS/PCE are shown in Fig. 3. NS particles
without PCE are tightly packed together due to the large specific
surface area and high surface energy (Fig. 3(a)) [27]. As shown in
Fig. 3(b)–(e), most of NS were well dispersed in the NS/PCE solu-
tion and the agglomeration was drastically decreased. As men-
Fig. 1. FT-IR spectra of NS, PCE and NS/PCE3.
tioned above, NS particles have been grafted onto the PCE
molecule, which would decrease the surface energy of NS. In addi-
tion, the polyether side chain of PCE could also serve as a barrier for
the agglomeration of NS.
Zeta potentials of NS and NS/PCE are shown in Table 3. Absolute
values of zeta potentials for NS/PCE1, NS/PCE2, NS/PCE3 and NS/
PCE4 were firstly increased and then decreased with the increase
of NS, and all of which were higher than that of NS. The higher
absolute value of zeta potential represents the higher electrostatic
repulsion and better dispersion stability of the system [28]. It is
indicated that the dispersion of NS could be improved in NS/PCE.
Molecular weight and its distribution of PCE and NS/PCE are
measured by GPC. According to GPC results in Table 4, Mw of NS/
PCE increases with the increase of NS, which might be caused by
the graft of NS on PCE chains. The copolymers of AA and TPEG
are polymerized with NS with the addition of NS particles, result-
ing in the large increase in Mw of NS/PCE. PDI value could be used
to evaluate the molecular weight distribution and polymerization
effect. It is reported that molecular weight distribution would be
much more uniform and polymerization effect would be much bet-
ter when the PDI value is closed to 1 [24]. As shown in Table 4, PDI
value of PCE, NS/PCE1, NS/PCE2 and NS/PCE3 are close with each
other, and it slightly increases with the increase of NS, which indi-
cates that most of NS has been grafted onto the PCE molecules in
this case. Further, PDI value of NS/PCE4 is greater than that of
the other samples and far from 1, which can be ascribed to the
strong crosslinking effect between the polymer and NS in the case
of excessive NS was added [29].
TG curves of NS/PCE are shown in Fig. 4. There is a large decom-
position peak between 380 and 600 °C for each sample, which is
attributed to the thermal oxidation and decomposition of polymer
[30]. Grafting content of NS in NS/PCE could be calculated accord-
ing to the Eq. (1),
G ¼ ðW 2  W 3 Þ=W 1  100% ð1Þ
where G denotes grafting content, W1 denotes the initial mass of
NS/PCE in percentage, W2 denotes the residual mass of NS/PCE in
percentage after 600 °C, and W3 denotes the residual mass of PCE
in percentage.
According to TG curves and Eq. (1), estimated grafting content
of NS in NS/PCE1, NS/PCE2, NS/PCE3 and NS/PCE4 samples is
4.23%, 8.48%, 13.36% and 13.11%, respectively. Grafting content of
NS in NS/PCE was firstly increased and then stabilized with the
increase content of NS during preparation of NS/PCE.
Based on the results obtained above, possible formation mech-
anism of NS/PCE is proposed and shown in Fig. 5. There are many
silicon hydroxyl groups on the surface of NS, and its concentration
is about 5 -OH/nm2 [18]. Hydroxyl group is reactive in aqueous
solution and can be substituted by many other functional groups
4 C. Ren et al. / Construction and Building Materials 252 (2020) 119037

Fig. 2. NS/PCE solutions after 30 mins and 3 days placing.

Fig. 3. TEM images of (a) NS, (b) NS/PCE1, (c) NS/PCE2, (d) NS/PCE3 and (e) NS/PCE4.

[31]. In an alkaline environment, PCE could be condensed with NS 3.2. Effect of NS/PCE on properties of fresh cement pastes
and would be anchored onto the surface of NS through Si-O- to
form the NS/PCE. Silicon hydroxyl in PCE molecular structure could be used as an
adsorption group to improve the adsorption capacity and so as to
improve the dispersion ability of PCE for cement particles
Table 3 [32,33]. It seems that the initial fluidity of cement pastes increased
Zeta potentials of NS and NS/PCE (mV). gradually with the increase of PCE or NS/PCE, and the maximum
NS NS/PCE1 NS/PCE2 NS/PCE3 NS/PCE4
initial fluidity would be obtained when 0.30% of PCE or NS/PCE
was added except for NS/PCE1 and NS/PCE4 (Fig. 6(a)). NS/PCE2
11.98 16.54 20.57 25.96 23.14
exhibited a higher fluidity than the other samples at the saturation
 C. Ren et al. / Construction and Building Materials 252 (2020) 119037 5

Table 4 which increased fluidity of cement pastes in a short time [16]. Flu-
Molecular weight of PCE and NS/PCE. idity of the pastes would be obviously decreased after 1 h, amounts
Samples Mn (g/mol) Mw (g/mol) PDI (Mw/Mn) of PCE have been consumed through chemical adsorption in the
PCE 17,820 21,550 1.210 initial stage, which might decrease the free PCE in cement pastes
NS/PCE1 36,260 46,900 1.293 and lead to the higher fluidity loss after 1 h.
NS/PCE2 37,060 48,670 1.313 Zeta potential of the cement pastes without water reducer
NS/PCE3 39,260 52,440 1.336 (sample blank) is positive as shown in Fig. 7, which increases
NS/PCE4 30,780 57,850 1.880
within 30 min and then decreases with time. Zeta potential of
the cement pastes will become negative with the addition of PCE
or NS/PCE. Absolute values of zeta potential for cement pastes con-
taining NS/PCE slightly increase before 1 h and then obviously
decrease over time (Fig. 7), which is consistent with the fluidity
results of cement paste over time. At the same dosage of water
reducer (PCE or NS/PCE), electronegativity of cement pastes con-
taining NS/PCE1 and NS/PCE2 was greater than that of the sample
containing PCE, which confirmed that the existence of carboxylic
acid and silicon hydroxyl groups contributed to the electronegativ-
ity of cement particles [36]. However, electronegativity of the
cement pastes containing NS/PCE3 and NS/PCE4 was less than that
of the sample containing PCE. Excessive NS would reduce the
adsorption amount of PCE. On the contrary, the adsorption of PCE
also hinder the reaction activity of NS [26]. The same results were
obtained in the previous paragraph (fluidity of the fresh cement
pastes).
Adsorption capacity of NS/PCE on surface of cement particles is
shown in Fig. 8. Adsorption quantity of NS/PCE on cement particles
increased with the increase of PCE or NS/PCE, and would be
Fig. 4. TG curves of PCE and NS/PCE. reached to saturated point when 60 PCE2 is superior to NS/PCE3
and NS/PCE4 (Fig. 3), so that the active adsorption sites provided
by NS would be comparatively higher than that of the other
point (0.3%). Fluidity losses over time of fresh cement pastes with samples.
0.15% PCE or NS/PCE are shown in Fig. 6(b). Fluidity of fresh cement Schematic adsorption mechanism of NS/PCE is displayed in
pastes containing NS/PCE2, NS/PCE3 and NS/PCE4 gradually Fig. 9. Adsorption in cement pastes containing PCE is mainly the
increased within 60 min and then decreased after 1 h, while fluid- electrostatic adsorption between carboxyl groups and positively
ity of fresh cement pastes containing PCE and NS/PCE1 decreased charged mineral particles (such as C3A) or adsorption of negatively
sharply over time. Sufficient silicon hydroxyl groups have been charged mineral surfaces (such as C3S and CH) by Ca2+ bridging
introduced into the main chain of PCE and increased the charge [37]. For the cement pastes containing NS/PCE, silicon hydroxyl
density, hence the electrostatic attraction between cement parti- group of NS/PCE can be dehydrated and condensed with the hydro-
cles and water reducer can be increased [34]. Such a functional xyl group on surface of cement particles, and then adsorbed in-situ
group can undergo a condensation reaction with Si–O bond in through chemical bonding [35]. Chemisorption is much stronger
cement through a chemical bond to generate a chemical adsorp- than electrostatic adsorption [37], so the adsorption amounts of
tion, which is favorable for the adsorption of NS/PCE on the surface NS/PCE would be higher than that of PCE. However, adsorption
of the cement particles. Conversely, excess silicon hydroxyl groups capacity for NS/PCE3 or NS/PCE4 was lower than that of PCE as
would cause non-uniform adsorption/desorption and weaken the shown in Fig. 8. Groups („Si–O–Si„) formed by dehydration
adsorption capacity of PCE [35]. In addition, polyether side chain and condensation between silicon hydroxyl and hydroxyl on sur-
of PCE and NS/PCE ensured the ductility of fresh cement pastes, face of cement particles would be desorbed under high pH, then

Fig. 5. Schematic formation mechanism of NS/PCE.

6 C. Ren et al. / Construction and Building Materials 252 (2020) 119037
Fig. 6. (a) Initial fluidity and (b) fluidity over time of the fresh cement pastes.
Fig. 7. Zeta potential of cement pastes containing PCE or NS/PCE.
Fig. 8. Adsorption amount of PCE and NS/PCE.
preferentially adsorbed on surface of the negatively charged min-
eral phase when the NS/PCE with excessive NS was added, which
would lead to the uneven adsorption in cement paste. In this case,
adsorption properties of the copolymer on surface of the cement
particles would be weakened due to the decrease of chemisorption
provided by silicon hydroxyl [38].
3.3. Effect of NS/PCE on cement hydration
TG curves of cement pastes curing at 3 d and 28 d are illustrated
in Fig. 10, respectively. Evaporation of adsorbed water below
105 °C, dehydroxylation of CH at 400–500 °C and decomposition
of CaCO3 at 600–800 °C in hardened cement pastes are generally
accepted [39,40]. Mass losses in the above three temperature
ranges are listed in Table 5.
It can be found that CH in cement pastes containing NS/PCE is
higher than that of the blank sample (without water reducer)
and the sample containing PCE after 3 d curing, which indicates
that NS/PCE promotes the early hydration and generated many
more CH. After 28 d curing, CH in cement pastes containing NS/
PCE is decreased with the addition of NS in NS/PCE. It can be
deduced that NS in NS/PCE could be gradually released and reacted
with CH due to its pozzolanic activity [41].
XRD patterns of the hardened pastes are presented in Fig. 11.
Unhydrated C2S (2h = 32.7°) and C3S (2h = 29.5° and 32.2°) are still
observed in the XRD patterns. Relative intensities of C2S and C3S
diffraction peak for hardened pastes containing NS/PCE are lower
than that of the blank sample (without water reducer) and the
sample containing PCE, which also indicates the hydration promo-
tion of NS/PCE for cement [42]. In addition, relative intensity of CH
diffraction peaks decreased obviously with the increased content
of NS in NS/PCE system, which corresponded to the TG results.
Hexagonal plate type CH crystals tend to aggregate and crystal-
lize with same orientation on the interface between cement paste
and aggregate [43]. Oriented CH crystals will weaken the interface
bond strength between the cement paste and the aggregate inter-
face, and then decrease mechanical properties of the hardened
cement paste. Orientation coefficient of CH crystal (RCH) could be
described as follows according to the previous study [44],
Ið001Þ
RCH ¼ ð2Þ
0:74  Ið101Þ
Where I(001) is the diffraction intensity of CH on (001) crystal plane
(2h = 18.1°), I(101) is the diffraction intensity of CH on the (101) crys-
tal plane (2h = 34.2°).
There is no oriented growth of CH crystals if the RCH is equal to
1, and RCH will be much greater than 1 if oriented growth of CH
crystals increased [42]. Fig. 12 shows the orientation coefficients
of CH calculated through Eq. (2) based on XRD results. Much lower
RCH has been observed for the pastes containing NS/PCE compared
to that of the blank sample or the paste with PCE, and the RCH
 C. Ren et al. / Construction and Building Materials 252 (2020) 119037 7

Fig. 9. Schematic representation for dispersion and adsorption: (a) PCE, (b) NS/PCE with appropriate NS and (c) NS/PCE with excessive NS.

Fig. 10. TG curves of cement pastes after 3 d and 28 d curing.

would further decreased with the increase of NS in NS/PCE. The Micro-morphology of cement pastes containing PCE and NS/PCE
reduction of RCH indicates that less CH would be grown in the same curing for 28 d is observed by SEM. As shown in Fig. 13, there are
direction, which is beneficial to the microstructure refinement and loose and porous structures in the blank sample, and hexagonal
the mechanical properties improvement of the cement matrix. flaky crystals are concentrated in the voids. Relatively compact
8 C. Ren et al. / Construction and Building Materials 252 (2020) 119037

Table 5
Mass losses in different temperature ranges of cement pastes (%).

Sample 3d 28 d
105 °C 400–500 °C 600–800 °C 105 °C 400–500 °C 600–800 °C
Blank 4.87 2.74 2.06 4.22 4.23 2.30
PCE 3.67 2.89 2.85 3.89 4.06 1.88
NS/PCE1 3.06 2.92 2.45 3.11 3.47 2.07
NS/PCE2 3.50 3.02 2.58 3.53 3.23 1.99
NS/PCE3 3.33 3.11 2.70 3.74 3.15 2.47
NS/PCE4 2.87 3.14 2.27 3.86 3.36 2.41

Fig. 11. XRD patterns of harden pastes after 3 d and 28 d curing.

structures are observed when PCE or NS/PCE was used. The quan-
tity of large pores and hexagonal flaky crystals are all further
decreased with the increase of NS in NS/PCE, the microstructures
become much denser and most of flaky particles embedded into
the dense C-S-H gels.
3.4. Mechanical properties of mortars
Mechanical properties of mortars are shown in Fig. 14.
It is observed NS/PCE significantly improved the mechanical
properties of mortars. The decreased w/c (Table 2) and well
dispersed cement particles in mortars containing PCE or NS/PCE
would increase the structure compactness and thus improve the
mechanical properties. Besides, the addition of NS would lead to
high polymerization of C-S-H gels [45]. Early mechanical property
of the mortar with NS/PCE is slightly higher (except for NS/PCE1
at 1 d) than that of the mortar with PCE. NS/PCE1 or NS/PCE2
with higher adsorption capacity (Fig. 8) might be preferential
adsorbed on surface of cement particles, which slowed the early
hydration of cement. NS would be released from NS/PCE with
cement hydration proceeded, pozzolanic reaction between NS
and CH contributed to the higher 28 d mechanical properties.
However, lots of NS could not be grafted onto PCE when excessive
NS was used for NS/PCE4, the agglomeration of NS might
decrease the cement particles dispersion and the mechanical
properties growth.

4. Conclusions

NS particles can be grafted onto the PCE molecule to form the

Fig. 12. Orientation coefficient of CH in cement pastes curing at 3 d and 28 d.
nanosilica-doped polycarboxylate superplasticizer. Adsorption
capacity, dispersion effect and further the water-reducing rate of
NS/PCE for cement particles could be increased due to the
increased charge density and adsorption groups, which was bene-
ficial to the improvement of workability and mechanical properties
of cement mortars. In addition, less oriented growth of CH crystals
were observed in cement pastes with NS/PCE, which might also
contribute to the mechanical properties increasement and
microstructure refinement.
 C. Ren et al. / Construction and Building Materials 252 (2020) 119037 9

Fig. 13. SEM images of harden cement pastes (a) without PCE and with (b) PCE, (c) NS/PCE1, (d) NS/PCE2, (e) NS/PCE3 and (f) NS/PCE4.

Fig. 14. (a) Compressive and (b) flexural strength of the mortars.

CRediT authorship contribution statement Acknowledgements

Chunrong Ren: Methodology, Investigation, Writing - original
draft, data curation. Li Hou: Formal analysis, Methodology,
Writing - original draft. Jun Li: Conceptualization, Methodology,
Visualization, Writing - original draft, Writing - review & editing.
Zhongyuan Lu: Conceptualization, Methodology, Validation,
Writing - review & editing, Supervision. Yunhui Niu: Funding
acquisition, Project administration.
This work was supported by Sichuan Science and Technology
Program (No.2019ZDZX0024), the open project from National
Engineering Technology Center for Insulation Materials (18kfjc05)
and the Postgraduate Innovation Fund Project by Southwest
University of Science and Technology (No.19ycx0022).
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