Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 21696−21711 www.acsami.org

Interface Properties of Nanosilica-Modified Waterborne Epoxy

Cement Repairing System
Bo Pang,†,‡ Yunsheng Zhang,*,†,‡ Guojian Liu,†,‡ and Wei She‡
†
School of Materials Science and Engineering and ‡Jiangsu Key Laboratory for Construction Materials, Southeast University, Nanjing
211189, China

ABSTRACT: Nowadays, numerous concrete structures are urgently needed to be repaired

and strengthened for the severe safety and durability of constructions. In this study, a novel
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type of silane-based interfacial coupling agent (ICA) is prepared by modifying the silane
coupling agent (SCA) with a hydrothermally treated nanosilica (HTNS). The effect of ICA
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on the cement hydration and crystalline form as well as the hydrolysis/condensation extent
of siloxanes is illustrated. The bonding strength, morphology and propagation of the
interface cracks, and the interfacial ductile fracture characterization are investigated. Besides,
the coupling mechanism of ICA in the repaired interface is explored. The results show that
HTNS effectively catalyzes SCA hydrolysis and condensation to form Si−O−Si bonding in a
neutral environment. The application of ICA on an old cementitious matrix not only
significantly improves the bonding strength and toughness of the repair interface, but also
mitigates the negative effect of dealcoholization of siloxanes on the hydration of the cement.
The repaired interface simultaneously exhibits stiffness, toughness, and multicracking
features in the process of straining. On a microlevel, ICA consumes portlandite during
cement hydration and finely crystallizes to form a layered plug structure at the repaired interface . With the continuous
dissolution of portlandite, the nanosilica in ICA forms a fibrous, stable product with ions and enhances the interfacial pore plug
effect.
KEYWORDS: cement, repair, silane coupling agent, nanosilica, waterborne, epoxy resin, interface

1. INTRODUCTION solutions. Therefore, the concrete repairing industry has been

As the most widely used construction material around the
world, concrete is used in major infrastructure projects such as
bridges, tunnels, dams, railways, and wharves. In recent
decades, the amount of concrete has started to mushroom
because of the rapid economic development and urbanization,
especially in China. As the serviced life of concrete extends,
however, numerous inevitable durability issues like cracks,
erosion of large-scale areas, or even collapse are frequently seen,
which have become a threat to the safety and reliability of
construction.1−3 The life expectancy of about 600 000 bridges
in America is 42 years, with an estimated $ 76 billion in need to
deal with the damage problems. From the ASCE’s Failure to
Act report on the costs of poor infrastructure, by 2020,
deficient bridges and pavements will cost $ 58 billion. If left
unattended, the costs would jump to $ 651 billion by 2040.
Recently, on March 07, 2018, the Senate Democrats have
unveiled a proposal to invest $1 trillion in American
infrastructure, which includes $140 billion to ensure Highway
Trust Fund solvency over the next decade plus an additional
$140 billion to repair the roads and bridges, and so forth.4
Similarly, the repair and retrofit costs are estimated at $67
billion for Chinese infrastructure in 2016.5 In Europe and some
Asian countries, the annual repair cost has exceeded the cost of
the newly built constructions.6 As the deterioration of the
present concrete constructions becomes more and more severe
with time, repair and retrofit become the most cost-effective
rapidly diversified and developed in recent decades. Various
repairing systems are springing up, such as cement-based
repairing system,7 polymer-based repairing system,8 cement−
polymer composite repairing system,9 steel plates10 and carbon
fiber repair system,11 and so forth. Epoxy mortar possesses less
shrinkage, superior mechanical strength and adhesion property,
high chemical stability, wide adaptability, and good workability.
Therefore, it is commonly used in the field of concrete
construction repairing.12−15
Since the 20th century, the utilization and production of
solvent-based resins have been restricted or even prohibited by
strict environmental protection laws and regulations all over the
world. The types of waterborne epoxy-modified cement-based
repair materials (WECM) showing excellent mechanical
performance and durability have been further explored and
applied.16−18 However, even if WECM contains a considerable
amount of waterborne epoxy resin (WEP), the organic−
inorganic bonding strength and ductility with old concrete are
still insufficient or have even become unstable in the presence
of water and cement, resulting in a weak and brittle bonding
interface between the old concrete and the repairing materials.
Under strain and continuous fatigue load, the interface becomes
Received: March 12, 2018
Accepted: May 4, 2018
Published: May 4, 2018

© 2018 American Chemical Society 21696 DOI: 10.1021/acsami.8b04092

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the stress-concentrated area and ends in failure. As the interface
issue is the main reason for the decrease in the bearing capacity
of the repaired structure and the exfoliation of repair material,
therefore, the bonding treatment between the old and new
concrete has become an inevitable challenge in the field of
construction repairing.19
The exposed surface of old concrete is mainly covered with
CaCO3 (calcite), C−S−H gel, Ca(OH)2 (portlandite), and so
forth with loose and porous structures. To form a sound and
firm binding with WECM, it is necessary to create an organic−
inorganic covalent bond with good wettability. Silane coupling
agents (SCA) are additives which can effectively create Si−O−
Si covalent bonds between the organic and inorganic
interfaces.20 By applying SCA, the interface bonding can be
promoted from mechanical binding and electrostatic adsorption
into a covalent bond. The application of SCA first appeared in
the surface treatment of rubber fillers, dental bonding, ceramic
modification, and so forth.21−24 In recent years, the research on
the application of SCA in the repairing of concrete structures
has also been reported. Dong et al.25 improved the performance
of the rubber-modified cement concrete by using SCA-coated
rubber particles. The compressive and split tensile strength of
the concrete-coated rubber improved by 10−20% compared
with the control group. The bond quality of the repaired
interfacial transition zone has been studied by Xiong et al.26
who used SCA aqueous solutions to coat the surface of the old
concrete matrix. They observed a noticeable increase in bond
strength as a result of the pull-off bond strength. Wang et al.27
evaluated the bond strength, microhardness, microstructure,
and surface morphology of the interface between the resin and
the cement paste. The results show that the coupling agent can
improve the interface bond strength from 54 to 117% at 7 days
to 28 days old. Stewart et al.28 used the X-ray photoelectron
spectroscopy and static contact angle measurements to study
the interaction between different SCA and the cured cement
paste. The results of an increase in the bridging silicon and
oxygen atoms relative to the untreated samples demonstrated
successful silane condensation and a covalent bond formation
between the cement paste and the silanes. Currently, the
recognized coupling mechanism is that the SCA molecules
interact with the remaining hydroxyl groups on the surface of
the old concrete to form a covalent bond, which promotes an
increase in the bonding strength.29,30 Besides, the siloxanes in
the SCA molecules work only if the Si−O−Si covalent bonds
are formed with the remaining hydroxyl groups on the bonding
surface under certain conditions.20,24,31 The current means of
using SCA on an old cementitious matrices, however, are
mainly direct coating or applying without modification, which
result in the formation of a large amount of alcohol produced
by hydrolysis. The hydration of cement is severely hindered and
delayed along with the alcoholization progress of SCA.
Thereby, an unsubstantial layer in the vicinity of the repair
interface is then formed to further weaken the bonding effect.
In summary, the interfacial modification is the key issue that
restricts the large-scale use of WECM as a structural repair
material and safeguards the service life of the repaired concrete
structures.
The above review features promising developments in SCA
that applying SCA on old cement paste could lead to a
promising new approach for the organic−inorganic interface
bonding. So far, the theoretical research studies on the bonding
mechanism of WECM mostly focus on the exploration from
macroscopic (mechanical properties, adhesion, durability, etc.)
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to micro−nanoscale (morphology, etc.); hence, it is still an
initial stage. On the one hand, avoiding the negative effects of
SCA on the chemical reaction of cement is necessary. On the
other hand, achieving the coupling effect of SCA and the
simultaneous promotion of cement hydration in a moderate
chemical environment is also a thorny problem. In the field of
cement-based building materials, although the application of
polymers has appeared long ago,32,33 the in-depth under-
standing and research of chemical structures and the chemistry
between the organic and inorganic surfaces still need to be
viewed scientifically and dialectically. The influence of SCA on
the hydration of cement, the morphology of the interface
cracks, the characterization of the ductile fracture, and the
coupling theory of SCA on the surface of the cement paste are
necessary to be studied. More importantly, as a cement-based
repair surface, the excessive generation of portlandite and
porous products will lead to the degradation of the interfacial
repair function because of more moisture residing at the
interface.34 The alcohols produced by directly using SCA will
further promote the degradation of the interfacial bonding. The
utilization and certification of the catalytic SCA hydrolysis by
the hydrothermally treated nanosilica (HTNS), the filling
effects of cracks at the repair interface, and the improvement of
the crystal structure and chemical structure of portlandite from
the chemical point of view are very important.
In this study, 3-glycidoxypropyltrimethoxysilane (GPTMS) is
applied as SCA. The nanosilica shows a high catalytic activity
on the properties of various types of silica−polymer
composites35,36 as well as the accelerating effects for the
beneficial calcium−silicate−hydrate (C−S−H) formation in
cement hydration.37,38 Therefore, the HTNS is prepared by
hydrothermally treating nanosilica to catalyze the hydrolysis
and condensation of SCA and prepare the interface coupling
agent (ICA) which not only significantly improves the bonding
strength and toughness of the repair interface, but also avoids
the negative effect of dealcoholization of SCA on the hydration
of the cement. To illustrate the effect of ICA on the cement
hydration rate, crystallinity, and hydrolysis/condensation extent
of siloxanes, the conductivity−temperature−salinity simulta-
neous test, X-ray diffraction (XRD), thermal gravimetric
analysis (TGA), nuclear magnetic resonance (NMR), Fourier
transform infrared (FTIR) spectroscopy, gel permeation
chromatography (GPC), and so forth have been used.
Meanwhile, the adhesive strength between the old cement
matrix and WECM has been studied in terms of tensile strength
and flexural strength after treating the matrix with ICA, WEP,
and ordinary portland cement (OPC). Furthermore, atomic
force microscopy (AFM), scanning electron microscopy
(SEM), and other means are used to characterize the
morphology, viscoelasticity, and so forth of the interfacial
properties in microdomains. The multiple cracking and crystal
evolution rules in the repair interface and characterization of
the coupling mechanism of ICA with cement paste at different
scales are further studied. This study provides support for the
development of efficient organic−inorganic interface bonding
materials in the field of architectural repair.
2. MATERIALS AND METHODS
2.1. Cement Paste Matrix and WECM Sample Preparation.
2.1.1. Cement Paste Matrix Samples. Step 1: OPC and water were
mixed with a constant water-to-cement (W/C) ratio of 0.29 into a
paste (stirring speed of 600 rpm, 10 min).
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Step 2: the paste was poured into the molds (2 cm × 2 cm × 8 cm,
and the tensile mold with a tensile cross-sectional area of 4 cm2 shown
in Figure 1b,c) and vibrated for 10 s.
% aqueous sodium hydroxide solution), and acidic solution (10 wt %
aqueous hydrochloric acid solution).40
Freezing−thawing aging tests: to evaluate the resistance of the
repaired samples to freezing and thawing damage, both freshwater and
salty water are considered. Ocean water was artificially prepared as a
substitute (compound/concentration, g/L; NaCl, 24.53; MgCl2·6H2O,
11.11; Na2SO4, 4.09; CaCl2, 1.16; KCl, 0.695; NaHCO3, 0.201; KBr,
0.101; H3BO3, 0.027; SrCl2·6H2O, 0.042; NaF, 0.003).41
Artificial light-aging tests: the resistance to light aging of all the
samples is tested by a Xenon Test Chamber (Q-SUN XE-3) in both
dry and moist conditions with reference to the standard ASTM D904-
99.42
Different interfacial agents containing OPC, ICA, commercial epoxy
interface agent (CEA) of Sikafloor EpoCem-81 type (A component)
and Sikafloor-156 type (B component) produced by Sika Corporation
U.S., and WEP of CYDW-100 type (A component) and CYDHD-220
type (B component) produced by Petroleum & Chemical Corporation
of China are prepared. Six samples were selected from each
experiment, and the errors were calculated. The main procedure of
each experiment is shown in Table 1.

Table 1. Main Procedure of Each Aging Experiment

freezing− artificial
immersion aging thawing light aging
test aging test test
water,
water, alkali substitute water,
Figure 1. Flow diagram of the ICA preparation and repairing solution, acidic ocean without
interfacial agent solution water water
procedure (a) and schematic diagrams of the tensile strength test (b),
flexural strength test (c), and slant shear strength test (d). OPC, ICA, CEA, WEP the samples are the condi-
placed in samples tion the
airtight boxes are test
containing frozen in samples
Step 3: the molded samples were placed under a curing condition of different water or for
98% relative humidity (RH) at 25 °C. corrosive salt 90 days
solutions for solution at a RH
2.1.2. WECM Samples. Step 1: OPC and water were mixed with a 90 days, from of 50
constant W/C ratio of 0.29 into a paste. 50 ± 3 °C 16 ± 2 and 98%,
Step 2: WEP was mixed with a matched hardener into a WEP to with the
mixture. − wave-
16 ± 2°C length of
Step 3: the WEP was mixed with the OPC paste with a polymer-to- within 340 nm,
cement (P/C) ratio of 0.4 within 20 min. Each mixing procedure 4 h and the
lasted for 10 min at a speed of 600 rpm. are irradi-
2.2. ICA Preparation. Step 1: HTNS−−nanosilica was mixed with thawed ance of
to 0.55 W/-
water with a ratio of 1:19 and stirred by a rotor at 80 °C for 8 h. 16 ± 2 °C m2, the
Step 2: SCA of 3-glycidyloxypropyltrimethoxy silane (GPTMS) within black
with a purity of 97 wt % was mixed with HTNS with a ratio of 1:1 and 2 h in a standard
stirred by a rotor at room temperature for 20 h. ICA was then single ther-
cycle, mometer
prepared. As a comparison, SCA and non-HTNS were mixed with the fresh of
same ratio as that of the control group (CICA). wate-
2.3. Repairing Procedure on a Cured OPC Matrix. Step 1: after r-300 cy-
the OPC matrix samples were tested by flexural or tensile tests, the cles,
failure section of the samples was cleaned with a brush. ocean
wate-
Step 2: the failure section was evenly sprayed with a layer of ICA r-100 cy-
with a spray can and put in the molds. cles
Step 3: after drying for 10 min at room temperature, the WECM
was poured on the failure section, after which the repaired samples
were placed under a curing condition of 98% RH at 25 °C.
The ICA preparation process and the repair process are shown in 2.5. Conductivity−Temperature−Salinity Simultaneous
Figure 1a. Test. To study the effect of HTNS and untreated SiO2 on the
2.4. Aging and Durability. The durability and antiaging hydrolysis performance of SCA and the effect of ICA on the hydration
properties of the repaired samples (shown in Figure 1d) are mainly of cement, the hydrolysis/hydration exotherm, conductivity, and
based on the slant shear strength of the samples before and after the salinity of SCA and cement in solution were investigated by the
aging tests (immersion aging tests, freezing−thawing aging tests, and conductivity−temperature−salinity simultaneous test. The SCA and
artificial light-aging tests). All the samples are with the cement paste ICA were formulated into a solution of 500 mg/mL. Then the SCA
matrix of 1 year old and repaired and cured for 28 days before all the solution was tested after the addition of distilled water (control),
tests. The slant shear strength test method refers to the standard test untreated SiO2 (CICA), and HTNS (ICA) immediately. The tests
method for bond btrength of epoxy-resin systems used with concrete, were ended after the conductivity was steady. Furthermore, the cement
ASTM C882/C882M.39 paste with a W/C ratio of 9 was tested by adding 1 mL of SCA and
Immersion aging tests: all the samples (repaired for 1 month) in the nanosilica emulsion mixture (paste−CICA), 1 mL of ICA (paste−
immersion aging tests are immersed in freshwater, alkali solution (5 wt ICA), and 1 mL of distilled water (paste−control). The conductivity,

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Figure 2. Conductivity, salinity, total dissolved solids, and temperature curves of (a) SCA with distilled water (control), (b) SCA with non-HTNS
emulsion (CICA), (c) SCA with HTNS emulsion (ICA), (d) cement paste (paste−control), (e) cement paste with untreated nanosilica emulsion
(paste−CICA), and (f) cement paste with ICA (ICA).
temperature, total dissolved solids, and salinity were tested in an
insulated box to prevent the impact of the environment.
2.6. FTIR−TG−XRD Analysis. FTIR spectroscopy was performed
by a FTIR spectrometer (Nicolet 5700) with a wave number range of
400−4000 cm−1 and resolution of 0.1 cm−1. To conduct the FTIR
measurements, 1 mg of the paste powder was mixed with 100 mg of
KBr to prepare slices.
The thermal behavior of the cement paste and nanosilica before and
after treatment was analyzed using a TGA (Netzsch, TG209 F3
model) equipment. All the tested cases were carried out under the
following conditions: 50 mg samples, heating temperature 10 K/min,
heating to 850 °C, platinum crucible, and 100 cm3 of ambient N2.
The crystalline phases were analyzed by means of XRD, using the
Bruker, D8-DISCOVER model equipment. The patterns were
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collected in the 2θ scan range of 10−70° using a step size of 0.02°
and a scan speed of 0.25 s/step.
2.7. Meso−Microscopic Morphology Analysis. To better
observe the crack growth and multicrack state at the interface layer
during fracture, two glass slides were treated with ICA and then
bonded together with a hardener. After 24 h, the bonded slides were
split at different speeds and observed under a digital reflective
polarizing microscope (Axioskop-40 Pol Zeiss) at the microscopic
scale.
The morphology and hydration products on the fractured surfaces
were observed and analyzed by SEM (FEI 3D) and energy-dispersive
spectroscopy (EDS).
2.8. NMR-GPC Analysis. 29Si and 1H NMR with a prepolymer of
PSR were performed using an AVANCE III HD 600 Bruker
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Figure 3. GPC curves of SCA hydrolyzed for 7 days in blank (a), distilled water (b), non-HTNS emulsion (c), and HTNS emulsion (d) at 25 °C.
spectrometer (Bruker, Switzerland) using deuterated chloroform
(ClD3) and deuterated water (D2O) as solvents.
Room-temperature GPC was carried out on a PL-GPC220
(Polymer Laboratories) equipped with a PL MIXED-C column
using tetrahydrofuran as the solvent and eluent.
2.9. Macromechanics−AFM Analysis. A force spectrum was
performed with tapping-mode and test-mode AFM to evaluate the
surface roughness and viscoelasticity of the interface before (surface
apply) and after fracture. Both topological and phase images were
recorded with a Dimension Icon model device. The data sampling rate
was 10 MHz and the scan size was 250−1000 μm2. The values of root-
mean-square roughness (Rq) and maximum height roughness (Rmax)
were calculated from the AFM images.
3. RESULTS AND DISCUSSION
3.1. Characterization of SCA Hydrolytic Condensation
and Cement Hydration. The hydrolysis and condensation
theories of SCA in acid/alkaline base have been extensively
studied and demonstrated.43,44 Okumoto45 brought up a
theoretical study that if the hydroxyl groups of the substrate
are solvated by other water clusters, the activation energies
could be very small. The hydrolysis of siloxanes in a neutral
environment is much slower than that in acidic and alkaline
environments. However, the acidic and alkaline environments,
on the other hand, will open the epoxy groups, resulting in a
reduced coupling efficiency.44 Therefore, the catalytic effect of
nanosilica was used to accelerate the hydrolysis rate of SCA,
and it was easier to eliminate alcohol before mixing with the
cement, thereby alleviating the negative effects. Thus, the
conductivity, salinity, total dissolved solids, and temperature of
SCA in different conditions have been tested to find out the
effect of hydrothermal treated/untreated nanosilica on the
hydrolysis of SCA and the effect of ICA on early cement
hydration. As the siloxane is hydrolyzed to silanol, methanol is
produced, and the conductivity increases with hydrolysis,
releasing heat. As shown in Figure 2a, the period of hydrolysis
equilibrium of SCA in water is up to 4 days. An obvious
exothermic peak at an early stage (0−4 h) is related to the
process of hydrolysis of the first siloxane group in the SCA
molecules. When one of the three siloxanes on a silicon atom is
hydrolyzed to a silanol group, the chargeability of the silicon
atom changes with the rate of hydrolysis slowing down. When
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the same reaction was triggered by adding 10 wt % CSCA, the
conductivity increased sharply, and the rate was 5 times faster
than that of the control (shown in Figure 2b). At 1000 min, the
exotherm was stabilized, although the reaction did not stop
completely. Therefore, it can be speculated that the hydroxyl
groups on the surface of nanosilica have an obvious catalytic
effect on the hydrolysis of SCA. However, at about 1100 min,
the final values of conductivity, salinity, and total dissolved
solids of the CICA sample were 25.21 μS/cm, 0.0063%, and
12.45 mg/L, respectively, which were less than the those of the
control (39.45 μS/cm, 0.0072%, and 19.34 mg/L). Therefore,
although SCA was catalytically hydrolyzed by nanosilica, the
hydrolysis of the first siloxane played a major role in the
exothermic peak, which reflected the reaction had not been
completely finished. For the case of ICA (Figure 2c), hydrolysis
and condensation of SCA were further promoted. The curves
show a strong correlation between temperature and con-
ductivity, which represents that the hydrolysis is dominant.
Because of the decrease in electrical conductivity, it is
concluded that the hydrolysis of SCA with HTNS is
accompanied by the condensation process. Three obvious
exothermic peaks are shown in the whole reaction process,
which probably represent the hydrolysis of the three siloxanes
in the SCA molecules. When the reaction was balanced at 1300
min, the values of conductivity, salinity, and total dissolved
solids of the ICA sample were 39.80 μS/cm, 0.0072%, and
19.91 mg/L, respectively. Compared with the control group,
the hydrolysis reaction was more complete, and the efficiency
increased by 3 times. From the start of the reaction up to about
1500 min, the values of the control sample, CICA sample, and
ICA sample were 1895, 1993, and 2366, respectively. It
demonstrates that the HTNS dramatically accelerates the
hydrolytic efficiency of SCA. The reason for this phenomenon
is that the hydrogen bonds of silanols adjacent to the surface
are opened after the hydrothermal treatment and replaced by
water clusters, which accelerate the density of the effective
hydroxyl groups and water clusters and enhance the catalytic
action of nanosilica.46,47 For the case of the cement paste with a
W/C ratio of 9.0 (Figure 2d), the curves of conductivity and
temperature directly reflect the hydration process of a clinker.
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Figure 4. 1H NMR spectra of SCA (a) in deuterated chloroform (CDCl3), 29Si NMR spectra (b), and 1H NMR spectra (c) of the fully hydrolyzed
products obtained by the reaction of GPTMS in deuterated water (D2O) with treated/untreated SiO2 for 7 days.
At the first 500 min, the temperature rose up sharply to 20.9
°C, which represented the heating from the dissolution of the
cement clinker minerals. Meanwhile, in the range of 0−1500
min, conductivity, salinity, and total dissolved solids showed a
distinct linear relationship with the changing temperature. In
this period (preinduction and induction of cement hydration),
the chemical changes of the solution were dominated by the
dissolution of the ions.48,49 Thereafter, the hydration of cement
entered the acceleration, deceleration, and stabilization periods
to form the second exothermic peak. The ions in solution
gradually formed the crystalline state from the saturated state,
the temperature rose, and the conductivity kept decreasing.49
When the cement was hydrated with the addition of 10 wt %
CICA (Figure 2e), methanol, which was slowly produced from
SCA hydrolysis, significantly prevented the hydration of the
cement. The conductivity rose slowly to about 6000 μS/cm in
3000 min. It was assumed that SCA, which was not hydrolyzed
completely, continued to hydrolyze throughout the cement
hydration. At 500 min, the hydration exotherm peak value was
about 20 °C, followed by an inconspicuous hydration
acceleration period. The methanol produced by SCA hydrolysis
had a less effect on the early dissolution of cement, but a greater
impediment to the formation of cement-hydrated minerals.
Moreover, because of a large amount of nonhydrolyzed SCA
present in CICA, a clear peak in hydrolysis exotherm appeared
before 100 min. For the case of ICA, compared with the paste−
control group, ICA obviously promoted the hydration of
cement (shown in Figure 2f). After a transient induction
period, the cement quickly entered the accelerated phase, and
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initial coagulation and curing were completed within 2000 min.
The temperature curve integrated value reached upon 6138
within 2000 min, which was close to 7145 of control cement
paste sample in 3000 min. There was only a small exothermic
peak within 100 min, indicating that only a very limited
hydrolyzed siloxane groups were involved in the ICA, which
minimizes the hindrance on the cement hydration by methanol.
To study the final hydrolyzate and the extent of hydrolysis of
SCA under diverse conditions, qualitative and quantitative
analyses were performed by NMR−GPC analysis. Figure 3
shows the GPC curves of SCA hydrolyzed for 7 days in blank,
distilled water, non-HTNS emulsion, and HTNS emulsion at
25 °C. To better distinguish the molecular weight (MW)
represented by each peak and the amount of each substance,
the results of the curve fitting analysis were applied to
differentiate each substance with different MW by different
colors, and then all the peak areas were calculated. The SCA in
the blank group (Figure 3a) was tested with the MW
distribution in the range of 200−260 (MW of GPTMS is
236.34). When the SCA was hydrolyzed with distilled water
(Figure 3b), three peaks with MW of 200−260, 370−450,
500−630, and 70−820 were observed in the GPC curve,
demonstrating that GPTMS hydrolyzed in water existed mainly
in four states, which were monomers, dimers, trimers, and
tetramers. The results are essentially consistent with those
studied by Gabrielli.44 The proportions of the hydrolysates
were 40.38, 7.63, 28.76, and 23.23%. Thus, 40.38% of GPTMS
is not fully hydrolyzed or unhydrolyzed at all. When untreated
nanosilica were present in the GPTMS hydrolysis system
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Figure 5. Flexural strength (a) and tensile strength (b) of the repaired samples by ordinary cement repair (OPC-modified), waterborne epoxy repair
(WEP-modified), and ICA-treated WECM repair (ICA-modified). Interfacial viscoelasticity (c) and roughness (d) before and after the fracture of
ICA-treated and WEP-treated cement paste surface. Slant shear strength (e) of samples after the aging test.

(Figure 3c), the composition of the final hydrolysates did not
change. However, the catalytic effect of nanosilica resulted in a
decrease in the GPTMS monomer (18.98%), with a significant
increase in the proportion of dimers (17.88%) and trimers
(42.64%). In contrast, HTNS greatly affected the final products
of the GPTMS hydrolysis system such that the final SCA
hydrolysates progressed to a state of pentamers (Figure 3d).
The proportions of monomers, dimers, trimers, tetramers, and
pentamers after SCA hydrolysis were 3.04, 3.84, 3.74, 6.74, and
82.64%, respectively. The incorporation of ICA accelerated not
only the degree of SCA hydrolysis but also the monomer
condensation rate. Moreover, the final hydrolysates retained the
activity as coupling agents because the hydrolysates eventually
exist as an aqueous dispersion of pentamers. Because of the
high stability of the final hydrolysates (no sedimentation within
6 months), the pentamers are generally assumed to exist in a
five-membered ring or other steady states.
The GPC results have shown further hydrolysis and
condensation of SCA and dispersed pentamers in the ICA
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system. To study the specific details of hydrolysis and
condensation of the siloxane groups before and after the
treatment, NMR was applied for further analysis. Figure 4a
shows the 1H NMR spectra of the specific molecular formula of
SCA. To avoid hydrolysis and determine the original molecular
formula of SCA, deuterated chloroform was used as the solvent.
The NMR peak assignments were in line with the reported
results.50 The scenarios of SCA with hydrothermal treated/
untreated nanosilica (SCA + treated SiO2/SCA + untreated
SiO2) and the control one (SCA + H2O) were carefully
monitored by using 29Si NMR analysis. As SCA was in various
hydrolysis states under different conditions after 7 days, the
peak intensity and chemical shift of the spectrum showed
variations (Figure 4b, Tn corresponds to the Si atom with a Si−
C bond and n bridging oxygen bonds −Si−O−Si−). The
results indicated that only a portion of the siloxane groups in
water was hydrolyzed to silanol moieties or formed −Si−O−
Si− structures with the unhydrolyzed monomers. The T1 peak
was significantly enhanced and the degree of hydrolysis
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Figure 6. AFM images and section tortuosity of the surface and fracture interface of waterborne epoxy repair (a,b) and ICA-treated WECM repair
(c,d).
increased with the addition of non-HTNS. Meanwhile, the
obvious T2 peak indicated the appearance of a hydrolyzed
diradical structure. However, the T0 and T1 peaks almost
disappeared when SCA was modified by HTNS. The minor
pronounced T2 and T3 peaks emerged, which indicated that the
siloxane groups in SCA were hydrolyzed and partially
condensed. Almost all of the siloxanes in the ICA are converted
to silanols in the form of methanol; this result is consistent with
the experimental research of Gabrielli et al.44 and the GPC data
of Figure 3. However, in the results of Gabrielli, a shift of the
two peaks of H6′ (δ = 2.75 ppm, dd, J = 4.2 and 2.6 Hz) and
H6′ (δ = 2.94 ppm, t, J = 4.2 Hz) to lower fields (δ = 3.64−
3.46 ppm), which was caused by the hydrolysis of the epoxide
ring, was observed.44 This phenomenon did not occur in the 1H
spectra (Figure 4 c). Therefore, not only were most of the
siloxane groups of SCA efficiently converted into methanol in
ICA, but the weak acid condition also avoided the consumption
of the epoxy groups. In the acidic and alkaline conditions,
although it can promote hydrolysis, the epoxy group is more
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unstable. Moreover, GPTMS will quickly form a solid state and
lose the coupling effect in a strong alkaline environment.44,51
3.2. Properties of Interfaces between the Old Cement
Paste and WECM. The final purpose of the repair interface
modification is to improve the prerequisite interface properties
of strength and toughness as well as the durability. Therefore,
the tensile and flexural strength were tested to compare the
repair effects by modifying the old cement paste matrix with a
fresh ordinary cement paste (OPC-modified), WEP-modified,
and ICA-modified. The viscoelasticity and roughness before
(modified surface) and after fracture (modified interface) were
compared by applying ICA and WEP. As the experimental
cement paste base was mixed with type 52.5 OPC at a low W/
C ratio of 0.29, the initial flexural strength and tensile strength
(black line) reached up to 13 and 3 MPa, respectively (Figure
5a,b). The repaired sample treated with the same type of OPC
paste as the interfacial component (gray line) exhibited the
same elasticity modulus but a lower strength (7.3 and 0.6
MPa), whereas a significant decrease in fracture ductility was
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Figure 7. Polarized transmitted light microscopy images of the fresh fracture interfaces with a splitting time of 2 (a) and 10 s (c). Image (b) of a
dried sample (a) at 100 °C for 24 h. In situ images (d) of the crack expansion process at the interface with A splitting time of 1 min.
observed after the repair. The treated WEP could improve the
resistance to ductility, but the lower modulus of elasticity and
strength made the sample more vulnerable to tensile stress (red
line). The ICA-modified interface prominently improved the
flexural and tensile ductility of the repaired sample, and the
failure process is divided into two stages. In the first stage, the
interface showed a stiffness similar to the cement matrix, which
was related to the incorporation of the cementitious materials
in WECM. In the second stage, the elastic modulus of the
sample decreased before fracture, which resulted in a higher
ductility and better mechanical properties. The ultimate
fracture strength was the same as with the cement paste
matrix, but the flexural and tensile ductility increased by 147
and 156%, respectively. The two-stage mechanical curve proves
the coupling effect between cement hydration and epoxy resin,
which is consistent with the previous research.52 From the
results of the AFM force−distance curves (Figure 5c), the WEP
and the fracture interface basically showed the same micro-
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mechanical properties. The stiffness exhibited by the WEP is
related to the higher brittleness of the epoxy resin itself. When
the interface was modified by ICA, the cement-based surface
brought out the obvious characteristics of both stiffness and
toughness. The stiffness phase of the viscous force curves had a
broader distribution. The smaller stiffness was related to the
nanosilica and cement hydrates, whereas the larger one was due
to the coupling effect of SCA. The fractured ICA-treated
interface showed a very strong viscoelasticity, which indicated
that the fracture process will consume a large amount of
fracture energy. The dissipation phase was directly related to
the ductile fracture and multiple cracking of the interface. The
Rmax, Rq, and Ra roughness values were calculated by the
interface parameters (Figure 5d). The roughness of the ICA
interface increased significantly after the fracture, whereas the
roughness of the WEP did not change much. The viscoelastic
and roughness data demonstrated that the ICA-treated interface
could form fractures at different dimensions and scales during
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Figure 8. FTIR spectra (a) and TGA curves (b) of dried (room temperature/24 h) samples of hydrothermal treated/untreated nanosilica and the
ones treated with SCA. FTIR spectra (c) and TGA curves (d) of dried (room temperature/24 h) cement paste (hydrated for 28 days) and the one
treated with ICA and SCA. XRD patterns of the ICA-treated/untreated cement paste hydrated for 28 days (e) and untreated/SCA-/ICA-treated
fully hydrated cement paste (f).

deformation to consume more fracture energy. Therefore, a
higher tolerance, toughness, and strength during impact and
sustained loading on the interface were achieved. The tolerance
of the interface bond to strain and stress is also reflected in the
durability of the repaired cement samples (shown in Figure 5e).
Compared with the control group, the shear bond strength
after different aging tests reflect that the repair interface
bonding is much more vulnerable to damage by the freezing
and thawing cycles, especially in the cases with salt solutions.53
During the experiment, five of the six WEP samples broke
through the interface in less than 100 cycles. This is related to
the limited bonding area created by the numerous air voids
(Figure 6a,b) in WEP. In the case of ECA, because of its strong
sealability and impermeability, its capacity for vapor pressure
and interface frost damage of the cement matrix has been
greatly reduced. This is also mentioned in its product
specification. Although the adhesion performance of ICA is
weaker for the initial adhesion than ECA, its durability and
comprehensive antiaging performance are even better. Besides,
21705
the ICA is competent for repairing the wet interface, and the
application of the ECA is greatly limited because of its
insolubility in water. As all the four repair cases were using
WEMC as the surface material, in which the cement
component protects the internal organic material from light-
aging damage, the comprehensive performance meets the
relevant standards for light aging.
The topography of the AFM images (Figure 6) validated the
conjecture of the causes of viscoelasticity shown in Figure 5. If
the cement matrix is directly repaired by WEP, because of the
low solid content of WEP, a lot of air voids with a diameter of
about 1 μm in the interface layer were formed (Figure 6a). As
the result, the effective bonding area was reduced by about
20%. In addition, the interface structure did not change
significantly when the WEP-repaired interface was fractured,
but only a few sporadic visible bulges were observed (height
difference of 30−40 nm shown in Figure 6b). This
phenomenon showed the lack of toughness cracking during
the progress of the interface failure. The AFM images of WEP
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verify the viscoelasticity results shown in Figure 5 that no
significant change is observed after the WEP interface fracture.
An obvious nanosilica was observed in the rough interface
treated by ICA which was assumed to improve the stiffness of
the repaired interface (Figure 6c). When an interfacial failure
was triggered, the appearance of an irregular rugged terrain in
the range of 20−120 nm was observed (Figure 6d). This is
directly related to the high viscoelasticity results of the ICA-
treated interface in the process of failure shown in Figure 5.
When a nanoindenter was used to test the bump area, a high
viscoelasticity curve was obtained. The bumpy interfaces also
verified the ductile fracture behavior and the consumption of
high fracture energies.
The macroscopic mechanical experimental results have
demonstrated that the interfacial treatment with ICA improved
the fracture toughness and bonding strength. To investigate the
specific process and the extent of crack propagation, two pieces
of ICA-treated glass slides were observed with a digital
reflective polarizing microscope at different splitting times.
When the interface was split within 2 s (Figure 7a), numerous
cracks were observed at an interval of 20−100 μm at the
fracture surface. Additionally, the crack propagation was
blocked and transformed into short cracks of 100−200 μm in
length. After zooming in, the crack stopped extending when
contacted with the fine cracks in different directions at the
interface. The sample in Figure 7a was dried to make the
interface coupling component shrink, and the change in the
base glass was observed. Numerous cracks were found (shown
in Figure 7b) in the base glass, consistent with the direction of
the interfacial crack propagation. As the untreated base glass
showed an almost brittle fracture during deformation without
any multiple cracking, this proved that the ICA induced
multicracks and brought a significant toughening effect onto the
interface as well as the substrate. For the case of the fracture
interface of splitting time within 10 s (Figure 7c), the
phenomenon of cracks blocking was not observed, but the
cracks still showed a multidirectional development and were
presented in various forms. To study the crack growth process
in situ, the sample was observed with a slow splitting loading
rate, and it was found that the cracks were developing by very
short leaps and bounds. Each crack grew in different directions,
and this phenomenon was associated with the blocking effect of
the internal nanosilica in ICA and the toughness brought by the
condensation of the coupling agent on the interface.
3.3. Characterization of Interfacial Chemistry Reac-
tion and Morphology. To quantitatively and qualitatively
characterize the hydrolytic condensation of SCA as well as the
catalytic action of nanosilica before and after the hydrothermal
treatment, various samples were tested by using TGA and
FTIR. Furthermore, the grafting efficiency of ICA and SCA on
the hydrated cement paste was further studied. The absorption
band (Figure 8a) at the scope of 3000−2800 cm−1 resulted
from the asymmetric stretching of the −CH bond from the
organic moieties of SCA.54 The strong and broad −OH
stretching vibrational absorption bands at 3300−3500 cm−1 are
derived from the water molecules. As all the samples were
evaporated to dryness at room temperature, the peak intensity
here may be related to the adsorbed water from the surface of
the nanosilica. It can be seen from the results that the −OH
peak intensity of the HTNS was relatively higher, and the
intensity of the −OH peak decreased after the reaction with
SCA, whereas the peak intensity of the −CH− absorption band
and the Si−O−Si absorption band (1000−1250 cm−1)
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increased significantly. Therefore, it can be proved that the
HTNS has a higher surface activity and a higher catalytic
efficiency. The reason may be related to the fact that after
hydrothermal treatment, the hydrogen bonds between the
vicinal silanol and germinal silanol on the silica surface were
broken and that the conjugated hydrogen bonds then are
formed with the surrounding water clusters.55 The increase in
the relative density of active silanol and water clusters enhanced
the catalytic effect on the hydrolysis and condensation of SCA.
The TGA results show that after hydrothermal treatment, the
adsorbed water molecules on the surface of the silica have been
increased by about 10 wt %, whereas those on the grafted SCA
increased from 0.9 to 4.4 wt % (Figure 8b). When the cement
paste samples of 28 days old were treated by SCA and ICA,
respectively, the peak intensity of −CH with the band range of
2800−3000 cm−1 and that of the Si−O−Si band increased to
some extent (Figure 8c). By comparing the absorption
intensity, the effect of the grafting treatment of ICA was
much more obvious than that of mixing SCA directly.
Moreover, after repeated experiments, it was found that the
sharp −OH peak (∼3600 cm−1, related to calcium hydroxide)
of the cement paste samples after treatment was reduced
apparently or even disappeared.52 Therefore, it was speculated
that calcium hydroxide in the cement paste had a direct
correlation with the grafting effect of ICA and SCA. To verify
the above conjecture, cement paste samples with a water-to-
cement ratio of 5:1 were hydrated in closed test tubes at 90 °C
for 7 days to obtain fully hydrated products. Then, the fully
hydrated cement samples were treated by ICA with the same
procedure. Then, the mineralogy of all the treated samples was
analyzed by XRD. The results of the TGA curves (Figure 8d)
demonstrated that ICA did indeed contribute to the
consumption of calcium hydroxide in cement paste, showing
that calcium hydroxide in the 28-day-old cement paste
decreased from 2.2 to 1.9 wt % and that the one in the fully
hydrated cement paste decreased from 15.1 to 2.9 wt % after
ICA treatment. The XRD results of mineralogy also certify the
depletion of portlandite by ICA. Evident portlandite diffraction
peaks appeared in the XRD patterns of the 28-day-old cement
paste, whereas they disappeared completely after ICA treat-
ment. The peak intensities of portlandite in the XRD patterns
of the fully hydrated cement paste increased significantly with
the disappearance of the C2S and C3S peaks (Figure 8f).
Therefore, the significant decrease of the portlandite diffraction
peaks further corroborated the consumption of calcium
hydroxide by ICA. Of course, calcium hydroxide should be
converted into other chemical forms such as C−S−H or into
the fine crystalline form that was hardly detected. In summary,
the consumption of portlandite is advantageous, relative to the
improvement of the interfacial properties, and the formation of
a low-strength portlandite is more likely to happen with a high
water−cement ratio at the interface and in the air voids.
The microstructures and coupling products at the micro-
meter−nanometer scale were further studied by SEM and EDS
analysis on the cement surface and the fracture bonding
interface. By comparing the treated and untreated bonding
interface transition zones (BITZ) at the longitudinal sections
with the same cement matrix, a visible crack throughout the
untreated interface was observed, whereas no evident crack was
observed at the ICA-treated BITZ. After zooming in situ, no
obvious bonding and crack arresting behavior were found in the
untreated interface with a crack width of 2−5 μm observed. For
the ICA-treated side, numerous fibrous products were found in
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Figure 9. SEM images of ICA-treated/untreated longitudinal section (a) and [(a)1,(a)2] of the cement paste BITZ after failure. SEM images of
cement paste surface before (b) and after (c) ICA treatment at 24 h. SEM images of the crack-filling effects of ICA at the longitudinal section of the
repair interface (d) and [(d)1,(d)2]. SEM images and EDX spot scan of the fracture section before (e) and after (f) ICA treatment repaired for 24 h
and 7 days.

the interface, which may be related to the crack arresting
behavior during the deformation. Compared with the smooth
portlandite crystals on the surface of the untreated cement
paste (Figure 9b), abundant coupling products (Figure 9c)
were attached to the surface of portlandite after ICA treatment.
When the repaired interface was fractured 24 h and 7 days after
repairing, respectively, a complex of a coral-like combination
21707
structure of cement hydration products and ICA-coupling
components was observed at the interface. To better observe
the crack-filling effect of ICA on the cement cracks and pores at
BITZ, the fracture surface of the fully dried cement paste was
treated with fresh ICA and the repair surface at the longitudinal
section was cut (Figure 9d). A clear crack blockage pattern
(shown in dotted lines) can be observed, and most of the
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Figure 10. Mechanism of the catalytic effect of hydrothermally treated nanosilica on SCA hydrolysis and condensation (a), fine-grained effect and
interfacial coupling effect of ICA on portlandite (b), and damage schematic (c) of the interface treated by different means.

interconnected cracks with a width of 1−3 μm at the interface
were plugged into ones less than 100 nm. After zooming in, the
cracks were filled with numerous nanosilica with a particle size
of 50−200 nm, which provided the reaction sites for the
formation of pore plugs by the subsequent chemical reactions
of ICA and the hydration products. After repairing for 24 h
(Figure 9e), this combination structure is a continuous
laminated sheet structure. By EDS analysis, it was observed
that the Ca content was as high as 53.84%, whereas the Si
content was 1.34%. Then it was speculated that it might be a
self-assembled composite structure of ICA coupling compo-
21708
nents and fine crystalline calcium hydroxide. After 7 days of
hydration (Figure 9f), the layered calcium hydroxide
disappeared, forming numerous fibrous coral structures. The
increase of Si content from 1.9% to above 7.2% in the EDS
results revealed that such a structure transforms into a C−S−H-
like structure or a more stable and insoluble calcium−silicon
composite structure.
On the basis of the above results and microscopic
morphology, the hydrolysis and condensation process of SCA
by HTNS and the possible coupling mechanisms of ICA are
inferred as shown in Figure 8. The surface properties of
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nanosilica have been studied extensively, and it is proved that
silanols are hydrogen-bonded to each other and/or to the
adsorbed water molecules.56,57 Orthosilanol is the smallest unit
of silicone polymer, and there are four silanol groups on the
surface without any intramolecular hydrogen bonds (IMHB)
(shown by blue dotted line). All hydrogen bonds can interact
with the surrounding monomers to further polymerize; hence,
this is also an important reason for their instability. When the
nanosilica branch number increases, most of the surface silanol
groups form IMHB with each other and reduce its catalytic
effect (Figure 10a). It is difficult to open IMHB by mechanical
means such as stirring and ultrasonic treatment, but hydro-
thermal treatment is very easy to cross the barrier. Moreover,
the surrounding clusters of water molecules readily form
hydrogen bonds with silanol immediately and result in the
stable clusters of water molecules on the surface of the
nanosilica. The catalytic effect of water clusters with different
molecule numbers on the hydrolysis and condensation of
alkoxysilanes has already been theoretically demonstrated by
Okumoto et al.45 Even under neutral conditions, water clusters
and hydrogen bonds with siloxanes can significantly reduce the
energy barrier of both hydrolysis and condensation, with a
silicon front-side nucleophilic attack and concomitant bonding
interchanges. According to the results from the portlandite
content, crystal structure, and SEM images, it is speculated that
ICA can transform a well-crystallized hexagonal plate to a fine-
grained near-square plate at the interface. Meanwhile, during
the polymerization of ICA and WEP and the hydration of
cement, lots of layered structures of a polymer−portlandite−
polymer is formed. This agrees well with the study of Galmarini
et al.,58 who simulated and synthesized the calcium hydroxide
structure formed in an aqueous solution. The structure of the
near-quartet is related to its lower surface energy. During the
recrystallization of calcium hydroxide, silanols are hydrogen-
bonded to the surface hydroxyl groups and dehydrated to
attach ionically to the (001) surface of calcium hydroxide. This
may be the reason for the sharp decline in the diffraction peak
at the (001) surface in the XRD results. During the continuous
dissolution of portlandite, the nanosilica in ICA forms a fibrous,
stable product with ions and enhances the interfacial pore plug
effect (as shown in Figure 9f). In contrast to the WEP- and
OPC-treated repairing interfaces (Figure 10c), the ICA-treated
samples were able to form stable fracture interfaces and
multidimensional cracking states upon fracture.
4. CONCLUSION
In this study, we use HTNS as a catalyst to promote the
hydrolysis of SCA. A novel and stable cement paste interface
coupling agent is prepared. The effect of SCA on OPC
hydration and the catalytic effect of nanosilica on SCA have
been studied for the first time. Second, the macroscopic and
microscopic mechanical properties and the fracture properties
of the repaired interface on the OPC surface are further
analyzed and studied.
The results prove that ICA significantly improves the
hydrolytic condensation efficiency of SCA and avoids the
negative impact of methanol generated during SCA con-
densation on cement hydration. The repaired interface
adhesion, stiffness, tenacity, and viscoelasticity are further
improved, while the interfacial cracks are filled with ICA to a
certain extent. Additionally, the effects of ICA on the
portlandite content and the crystal structure at the interface
have been first observed, and the coupling mechanism is
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speculated based on the morphology of the layered structure
and the atomic arrangement of the crystal and the coupling
agent.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: zhangys279@163.com.
ORCID
Yunsheng Zhang: 0000-0001-5630-4570
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support from
973 National Basic Research Program of China (no.
2015CB655102), and National Natural Science Foundation of
China (51678143). The authors thank Prof. Henmei Ni for
providing the experimental equipment and solutions.
■ ABBREVIATIONS
SCA, silane coupling agent; ICA, interface coupling agent;
ECA, commercial epoxy interface agent; WEP, waterborne
epoxy resin; WECM, waterborne epoxy-modified cement-based
repair materials; GPTMS, 3-glycidoxypropyltrimethoxysilane;
HTNS, hydrothermally treated nanosilica; OPC, ordinary
portland cement.
■
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DOI: 10.1021/acsami.8b04092
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21711 DOI: 10.1021/acsami.8b04092

ACS Appl. Mater. Interfaces 2018, 10, 21696−21711