nanomaterials
Article
Study of Dispersion, Hydration, and Microstructure of
Graphene Nanoplates-Modified Sulfoaluminate Cement Paste
Kai Cui 1 , Jun Chang 1, *, Mohanad Muayad Sabri Sabri 2
Citation: Cui, K.; Chang, J.; Sabri,
M.M.S.; Huang, J. Study of
Dispersion, Hydration, and
Microstructure of Graphene
Nanoplates-Modified Sulfoaluminate
Cement Paste. Nanomaterials 2022, 12,
2708. https://doi.org/10.3390/
nano12152708
Academic Editor: Csaba Balázsi
Received: 29 June 2022
Accepted: 4 August 2022
Published: 6 August 2022
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Copyright: © 2022 by the authors.
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distributed under the terms and
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Nanomaterials 2022, 12, 2708. https://doi.org/10.3390/nano12152708
and Jiandong Huang 3, *
1 School of Civil Engineering, Dalian University of Technology, Dalian 116024, China
2 Peter the Great St. Petersburg Polytechnic University, 195251 St. Petersburg, Russia
3 School of Civil Engineering, Guangzhou University, Guangzhou 510006, China
* Correspondence: mlchang@dlut.edu.cn (J.C.); jiandong.huang@hotmail.com (J.H.)
Abstract: Low-carbon ecological cement composites are among the most promising construction
materials. With low energy consumption, low carbon dioxide emissions, and high early strength,
sulfoaluminate cement (SAC) is a low-carbon ecological building material. In addition, graphene
nanoplates (GNPs) exhibit excellent performances. In this study, GNPs were dispersed by a combi-
nation of dispersant and ultrasonic treatment, and the dispersion effect of GNPs was characterized.
The effect of GNPs on the hydration process and products of SAC was studied, revealing that GNPs
accelerate SAC hydration. The hydration heat and ICP results showed that in the SAC hydrolysis
stage, C4 A3 Š (ye’elimite) hydrolyzed and released Ca2+ . GNPs absorbed the Ca2+ , and the Ca2+
concentration around C4 A3 Š decreased, which would promote the hydrolysis of C4 A3 Š and release
more Ca2+ , accelerating the hydration of SAC and the nucleation effect of GNPs, and providing sites
for the formation of hydration products. The analysis of XRD (X-Ray Diffraction) and TGA (Thermal
Gravity Analysis) showed that GNPs promoted the hydration of SAC and formed more AFt (ettrin-
gite) and AH3 (gibbsite). The generated hydration products fill the pores of the matrix and are closely
connected to the GNPs to form a whole, which improves the cement matrix’s mechanical properties.
Keywords: sulfoalumintae cement; dispersion; microstructure; hydration
1. Introduction
More than 4.2 billion tons of cement, the world’s largest artificial building material, is
produced annually, emitting a large amount of carbon dioxide; OPC (Ordinary Portland
cement) accounts for the majority of this. The amount of carbon dioxide emissions of
sulfoaluminate cement is 20–30% lower than that of OPC, and the firing temperature is
200 ◦ C lower than that of OPC. SAC is a low-carbon ecological cement-based material
widely used in emergency repair and construction, military engineering, unique engi-
neering, and marine engineering [1–3]. With the widespread use of building materials,
higher requirements are placed on the performance of materials, and the high brittleness of
cement-based materials limits their applications. The development of micro-cracks can lead
to the failure of cement-based materials. Therefore, controlling micro-cracks in the matrix is
crucial to improving the performance of cement-based materials. Researchers have added
steel fibers and nanomaterials to enhance the toughness of the matrix [4,5]. Commonly
used nanomaterials are graphene, carbon nanotubes, carbon fibers, nano calcium carbonate,
and nano-silica [6–10]; widely used fibers are steel fiber, PVA (Polyvinyl alcohol) fiber, and
basalt fiber [11–13].
Graphene nanoplates (GNPs) are the basic structural units of graphite materials of all
sizes. GNPs are composed of a single layer of carbon atoms wrapped in a two-dimensional
honeycomb framework, which can form 0D fullerenes, curled into 1D carbon nanotubes,
and stacked into 3D graphite. Compared with other carbon nanomaterials, GNPs have
unique advantages. GNPs are two-dimensional nanomaterials with a larger specific sur-
face area than carbon nanotubes [14–17]. GNPs have excellent mechanical, thermal, and
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2022, 12, 2708 2 of 12

electrical properties; the tensile strength of GNPs is 135 GPa, and their Young modulus
is 1.0 TPa, showing better advantages in terms of concrete properties [18,19]. The many
advantages of graphene make it a widely used building material [20]. When applying
GNPs to concrete materials, the first factor to consider is the dispersion of GNPs. Currently,
the commonly used dispersion methods include physical and chemical dispersion. Physical
dispersion includes dry mixing, ball milling, and combining the surfactant with ultrasonic
dispersion [21]. Chemical dispersion is mainly achieved by changing the atomic struc-
ture of graphene and introducing functional groups on GNPs through covalent chemical
modification to improve the dispersion of GNPs in water [21]. The oxygen-containing
functional groups of graphene significantly enhance the dispersibility of graphene in water,
and uniformly dispersed GNPs can improve the mechanical properties of cement-based
materials to varying degrees. Many researchers have studied the effect of GO (graphene
oxide) on the properties of cement-based materials. Lv et al. found that GO can adjust the
hydration products to form a denser microstructure. In addition, it was found that GO can
fill the pores of the cement matrix and has a self-healing effect on cracks [22]. Wang et al.
studied the mechanism behind GO promoting cement hydration. The oxygen-containing
functional groups react with CH (calcium hydroxide) and GO closely embedded in the
cement-based material to form a 3D network structure, effectively improving the cement-
based composite material’s mechanical properties [23]. Xu et al. showed that GO reacted
with hydration products to improve the compressive and flexural strength. The strength
improvement is not limited to the advancement of hydration, but GO consumes Ca2+ and
generates a new hydration product [24]. Zhao et al. investigated the effect of GO on the
hydration kinetics, mechanical properties, and microstructure of C-S-H (calcium silicate
hydrate). They found that GO could accelerate cement hydration, optimize pore structure,
and intercalate into the interlayer space of C-S-H gels through ionic bonding with Ca2+
and fill the gel pores [25]. Gao et al. found that GO provided a nucleation point for the
hydration reaction and accelerated the hydration of cement [26].
However, GO showed a reduction in the mechanical properties of graphene, including
the elastic modulus and tensile strength, and the strengthening and toughening effects
are not as sound as those of graphene. Many scholars have also studied the properties of
graphene-enhanced cement-based materials. Du et al. found that GNPs could improve
the permeability resistance of mortar and reduce the intrusion of water and ions [27]. Vo
et al. studied the effect of GNPs with different particle sizes (5 µm, 43 µm, 56 µm, and
73 µm) on cement mortar’s compressive strength and tensile strength, which increased
cement hydration due to the effect of van der Waals forces between GNPs [28]. Tang
et al. found that a sulfonate graphene nanosheet delayed the dissolution and induction
phases of the C3S (Calcium silicate) and hindered the hydration reaction [29]. Yao et al.
proposed a method for the in situ growth of graphene on cement particles. The graphene
is uniformly dispersed in the cement matrix, promoting the hydration process, forming a
denser microstructure, and improving cement-based materials’ mechanical properties [30].
Various studies have shown that GNPs can effectively improve the macro perfor-
mance of Portland cement-based materials by promoting the hydration process of cement.
However, some scholars have also pointed out that GNPs delay the hydration process of
cement-based materials and reduce the degree of hydration. Different studies have con-
flicting conclusions. The hydration mechanism of GNPs when reinforcing cement-based
materials has not been entirely determined. There is no sufficient in-depth and systematic
scientific explanation and no unified standard for the dispersion and characterization of
GNPs. In addition, the current related research is all based on Portland cement-based
materials, and there is a lack of research on low-carbon ecological SAC. As we all know, the
main mineral compositions of sulfoaluminate cement are C4 A3 Š and C2 S. In the absence
of gypsum, C4 A3 Š reacts with water and forms AFm (monosulphoaluminate) and AH3
(aluminum hydroxide), as shown in Formula (1), this reaction is very rapid and violent.
Usually, to control the reaction speed of cement, gypsum is added; in the presence of gyp-
Nanomaterials 2022, 12, 2708 3 of 12

sum, C4 A3 Š reacts with water, and gypsum forms ettringite (AFt) and AH3 ; this reaction is
shown in Formula (2).

C4 A3 S + 18H → C4 ASH12 + 2AH3 (1)

C4 A3 S + 2CSH2 + 34H → C6 AS3 H32 + 2AH3 (2)

Based on this, this paper focuses on the effect of graphene after dispersion on the
properties of SAC paste. SEM (Scanning Electron Microscope) and TEM (Transmission
Electron Microscope) were selected to characterize the dispersion effect of GNPs, and the
impact of GNPs on the microstructure of SAC cement-based materials is studied. The effect
of the concentration of GNPs on SAC hydration products was analyzed by XRD (X-Ray
Diffraction) and TG (Thermal Gravity Analysis). Finally, we explored the underlying
mechanism of GNP-enhanced SAC hydration. The results of this study will contribute to
future research on using GNPs as additives in cement composites to improve the properties
of cement-based materials. Since adding GNPs improves the mechanical properties of
cement, it is beneficial to expand the use of SAC. The widespread use of SAC, a low-carbon
ecological cement, would be beneficial for reducing carbon dioxide emissions, which is
advantageous to the economy and society.

2. Materials and Methods

GNPs (graphene nanoplatelets), produced by XG science, Inc. (Lansing, MI, USA),
the physical parameter is shown in Table 1. SAC (Sulfoaluminate Cement), provided by
Tangshan Polar Bear Building Material Co., Ltd. (Tangshan, China). The grade of cement
is 42.5. The XRD pattern of SAC and GNPs is shown in Figure 1. The physical properties
are shown in Table 2. A polycarboxylate superplasticizer, produced by San sheng Co., Ltd.
(Chongqing, China), was used to ensure the workability of cement paste. CO890, provided
by Sigma Aldrich, Co. (St. Louis, MO, USA), was used to disperse GNPs. CO890 is a
non-ionic surfactant with a hydrophobic group and a hydrophilic group. The hydrophobic
group is adsorbed onto the surface of GNPs, and the hydrophilic group penetrates deep into
the aqueous solution. It can prevent the intermolecular agglomeration of GNPs through
the steric hindrance effect.

Table 1. Characteristics of GNPs.

Thickness Surface Area Density Particle Purity

Type
(nm) (m2 ·g−1 ) (g/cm3 ) Diameters (µm) (%)
GNPs-M25 6–8 120–150 <3 25 >99.5

The dispersants with different dosages were weighed and poured into a beaker con-
taining 50 mL of deionized water. The mixture was stirred using a glass rod to dissolve
the CO890 and subjected to an ultrasonic treatment to disperse the solution. Next, 5 mg
of GNPs was poured into the aqueous dispersant solutions under mechanical stirring for
1 min and ultrasonic treatment for 10 min, with an output power of 360 W. Finally; an
ultraviolet spectrophotometer was applied to characterize the dispersion effect of GNPs.
The water to cement ratio is 0.28 (mass ratio), the dosage values of GNPs are 0.0.06%, 0.09%,
and 0.18% of the cement weight, and the sample names are marked as G0, G1, G2, and
G3. The dispersion liquid was mixed with SAC, poured into the stirring pot, stirred at
low speed for 2 min (rotation speed of 140 ± 5 r/min; revolution speed of 62 ± 5 r/min)
and then at high speed for 2 min (rotation speed of 285 ± 10 r/min; revolution speed of
125 ± 10 r/min. Finally, the paste was poured into a 4 × 4 × 16 cm3 mold curing for 1d,
and the mold was removed and cured for 28 days in a standard curing condition. Finally,
the mechanical properties, including compressive and flexural strength, were tested.
aterials 2022, 12, x
Nanomaterials 2022, 12, 2708 4 of 13 4 of 12

of XRD
Figure 1.
Figure 1. XRD pattern SAC pattern of SAC and GNPs.
and GNPs.

Table 2. The physical properties of SAC.

The dispersants with different dosages were weighed and poured into a beaker con‐
taining 50 mL of deionized water. The mixture was stirred using a glass rod to dissolve Compressive
Loss on Setting Time (min) Specific Surface Area Density Flexural Strength (MPa)
Ignition (%)
the CO890 and subjected to an ultrasonic
(m2 /kg)
treatment to disperse the solution. Next, 5 mgStrength
(g/cm3 )
of (MPa)
GNPs
Initial was poured
Setting into the aqueous dispersant solutions under
Final Setting 3d mechanical
28 d stirring3 dfor 28 d
1.4 32 56 ≥
1min and ultrasonic treatment for 10 min, with an output power of 360 W. Finally; an
350 3.1 6.3 7.2 42.5 47.2

ultraviolet spectrophotometer was applied to characterize the dispersion effect of GNPs.

The water to cement UV-VISratiowith is 0.28 (mass ratio),
a wavelength the nm
of 260 dosage
was values
appliedoftoGNPs determineare 0.0.06%,
the optimal dosage of
0.09%, and 0.18% of the cement
dispersant; weight, and and
the microstructure the sample
morphologynamesofare GNPsmarked
before as and
G0, G1,
afterG2, dispersion were
and G3. The dispersion liquid was mixed with SAC, poured into the
observed by FE-SEM (FEI Qunata450450, USA) and TEM (FEI Tecnai G2 F30, USA). The stirring pot, stirred
at low speed for Tam2 air
minC80 (rotation speed of 140(TA
microcalorimeter ± 5instruments
r/min; revolution
company) speedwas of 62 ± 5 to
used r/min)
test the hydration
and then at high process
speedoffor SAC2 min with and without
(rotation speed of GNPs.
285 ± ICP-OES (Perkin Elmer
10 r/min; revolution speed Optima
of 125 2000DV) was
± 10 r/min. Finally,used to thetest
pastethe wastotalpoured
concentration
into a 4of× Al3+
4 × 16and
cm3Ca2+.
mold Hydration
curing for 1d, products
and the were measured
mold was removed by XRD and(Bruker
cured D8 for ADVANCE
28 days in a diffractometer)
standard curingatcondition.
a 40 kV and a 40 mA
Finally, the operating
me‐ current,
chanical properties,respectively.
including EVA software was
compressive andused to detect
flexural hydration
strength, products. TG analysis (Mettler
were tested.
UV‐VIS with Toledo TGA/DSC1,ofSwiss)
a wavelength waswas
260 nm used to detect
applied to the hydration
determine thesample’s
optimal weight
dosageloss process at
different temperatures. The test temperature ranged from 50 ◦ C to 1000 ◦ C, with a heating
of dispersant; the microstructure and morphology of GNPs before and after dispersion
were observedrate by of 10 ◦ C/min,
FE‐SEM and the protective
(FEI Qunata450450, USA) gas was
and TEMnitrogen.
(FEI Tecnai G2 F30, USA).
The Tam air C80 microcalorimeter (TA instruments company) was used to test the hydra‐
3. Results Discussion
tion process of SAC with and without GNPs. ICP‐OES (Perkin Elmer Optima 2000DV)
was used to test 3.1.the
Dispersion of GNPs
total concentration of Al3+ and Ca2+. Hydration products were meas‐
Figure 1 shows
ured by XRD (Bruker D8 ADVANCE diffractometer) the XRD pattern of GNPs.at a 40 The
kV anddiffraction
a 40 mA peaks of carbon appeared
operating
◦
at 26 , 44 ◦ , and ◦
54 . It canused
be concluded from the products.
diffraction
current, respectively. EVA software was to detect hydration TGpeak intensity that the
analysis
(Mettler Toledo purity and crystallinity
TGA/DSC1, Swiss) was ofused
GNPs were very
to detect high. Figure
the hydration 2 presents
sample’s weightthe FTIR spectrum
loss
−1
process at different temperatures. The test temperature ranged from 50 °C to 1000 °C, with at 3435 cm
of GNPs. GNPs displayed absorption peaks of -OH and -COOH, located
− 1
a heating rate and of 101636 cm and
°C/min, , respectively. In addition,
the protective there was a C-O-C stretching vibration peak at
gas was nitrogen.
1117 cm−1 . According to previous studies [14], CO890 was the dispersant, the concentration
of CO890 ranged from 0.3 g/L to 1.0 g/L, and the absorbance of GNPs dispersion liquid
3. Results Discussion
with different concentrations was measured. As depicted in Figure 3a, the absorption peak
3.1. Dispersion of GNPs
at 260 nm and the absorbance of dispersion liquid showed an increasing trend along with
Figure 1 shows
the changethe XRD of CO890pattern of GNPs.
content. When Thethe diffraction peaks of
concentration of carbon
CO890 appeared
was 0.6 g/L, as shown
at 26°, 44°, andin54°. Figure 3b, the absorbance of GNPs reached the maximum that
It can be concluded from the diffraction peak intensity value theofpurity
1.271. According to

Nanomaterials 2022, 12, 2708
GNPs were very thin. SAED (Selected Area Electron Diffraction) was used to
GNPs. From the SAED pattern, as shown in Figure 5a, it was observed that the GN
crystalline, indicating that the GNPs were of high quality. From the SAED patter
ure 5b, it was observed that the GNPs showed typical hexagonal diffraction
5 of 12 spo
cating single crystal characteristics of GNPs.

the Beer-Lambert Law, we can characterize the dispersion I r degree of GNPs in the solution.
A  log(dispersion
As depicted in Formula (3), GNPs have an excellent )  ECLeffect. Figure 4a exhibits
the morphology of GNPs before dispersion; they have aIlayered s structure and are stacked
and twisted, their edges are curled and raised, and their surface is rough. Figure 4b shows
an SEM image of GNPs after dispersion; the layered structure of GNPs was thinner, and
where
the E edges
curled is a constant,
were moreCopen,
is thewhich
solution
was aconcentration,
benefit for bondingandhydration
L is the products.
optical path len
TEM was used to evaluate the quality of GNPs. Figure 5a,b show the TEM image of GNPs
after dispersion.
According GNPs were
to the multilayered
literature [31],and
thecurled,
actualwith wrinkled sheets,
concentration valueindicating
of GNPs in th
that GNPs were very thin. SAED (Selected Area Electron Diffraction) was used to scan
sion can be calculated according to the ultraviolet absorbance. It is generally belie
the GNPs. From the SAED pattern, as shown in Figure 5a, it was observed that the GNPs
the higher
were theindicating
crystalline, absorbance value,
that the GNPsthe higher
were thequality.
of high actualFrom
concentration of GNPs, in
the SAED pattern
inthat the5b,
Figure dispersion of GNPs
it was observed is improved
that the GNPs showed[14].
typical hexagonal diffraction spots,
indicating single crystal characteristics of GNPs.

Ir
A = log( ) = ECL (3)
Is

where E is a constant, C is the solution concentration, and L is the optical path length.

1636
1117

3435

3500 3000 2500 2000 1500 1000 500

Nanomaterials 2022, 12, x Wavenumbers/cm-1 6 of 13

Figure
Figure 2. FTIR
2. FTIR analysis
analysis of GNPs.
of GNPs.

Figure
Figure 3.
3. The
The dispersion ofGNPs:
dispersion of GNPs:(a)
(a)UV-VIS
UV‐VISofofGNPs
GNPs dispersions;
dispersions; (b)(b) absorbance
absorbance of GNP
of GNP disper‐
dispersions.
sions.
Nanomaterials 2022, 12, 2708 Figure 3. The dispersion of GNPs: (a) UV‐VIS of GNPs dispersions; (b) absorbance of6 of
GNP12 disper

sions.

Figure 3. The dispersion of GNPs: (a) UV‐VIS of GNPs dispersions; (b) absorbance of GNP disper‐
sions.

Figure 4. SEM
Figure of GNPs:
4. SEM (a)(a)before
of GNPs: before dispersion;
dispersion; (b)(b) after
after dispersion.
dispersion.

Figure 5. TEM images of GNPs after dispersion.

Figure 5. TEM images of GNPs after dispersion.

3.2.
Figure 5.Macro
TEM Performance
According
images to the literature
of GNPs after[31], the actual concentration value of GNPs in the disper-
dispersion.
sion can be calculated
Figure 6 shows the according
mechanicalto the ultraviolet
properties absorbance.
of the SAC paste.It The
is generally
additionbelieved that
of dispersed
the
GNPs higher the
improves
3.2. Macro Performanceabsorbance
the value,
mechanical the higher
properties the
of actual
the SAC concentration
paste. The of GNPs,
compressive indicating
strengths
that
of thethe dispersion
G0, G1, G2, andof GNPs is improved
G3 groups [14]. for 28d were 81.5 MPa, 89.7 MPa, 96.8 MPa,
after curing
Figure 6 shows the mechanical properties of the SAC paste. The addition of dispersed
GNPs 3.2.improves
Macro Performance
the mechanical properties of the SAC paste. The compressive strength
of the G0,Figure 6 shows
G1, G2, andthe
G3mechanical properties
groups after curingoffor
the 28d
SAC were
paste. 81.5
The addition of dispersed
MPa, 89.7 MPa, 96.8 MPa
GNPs improves the mechanical properties of the SAC paste. The compressive strengths
of the G0, G1, G2, and G3 groups after curing for 28d were 81.5 MPa, 89.7 MPa, 96.8 MPa,
and 94.5 MPa, respectively. Compared with the G0 group, the compressive strengths of G1,
G2, and G3 were increased by 10.1%, 18.8%, and 16.0%, respectively. When the content of
GNPs is 0.09%, the compressive strength of SAC pastes at its highest. When the content
of GNPs is 0.18%, the growth rate of compressive strength decreases, which may be due
to the agglomeration of GNP in the matrix when the content of GNPs is high, therefore
reducing the interface bonding between GNPs and the cement paste. The flexural strengths
of the G0, G1, G2, and G3 groups after curing for 28d were 6.85 MPa, 7.74 MPa, 9.87 MPa,
and 9.46 MPa, respectively. Compared with the G0 group, the flexural strengths of G1, G2,
and G3 were increased by 13.0%, 44.1%, and 38.1%, respectively. The changing trend of
flexural strength is similar to compressive strength. When the content of GNPs is 0.09%,
the flexural strength of SAC pastes at its highest.
 to the agglomeration of GNP in the matrix when the content of GNPs is high, therefore
reducing the interface bonding between GNPs and the cement paste. The flexural
strengths of the G0, G1, G2, and G3 groups after curing for 28d were 6.85 MPa, 7.74 MPa,
9.87 MPa, and 9.46 MPa, respectively. Compared with the G0 group, the flexural strengths
of G1, G2, and G3 were increased by 13.0%, 44.1%, and 38.1%, respectively. The changing
Nanomaterials 2022, 12, 2708 7 of 12
trend of flexural strength is similar to compressive strength. When the content of GNPs is
0.09%, the flexural strength of SAC pastes at its highest.

120 15
Compressive strength
14
Flexural strength
100

Compressive strength(MPa)
13

Flexural strength(MPa)
12
80 11
10
60
9
40 8
7
20 6
5
0 4
G0 G1 G2 G3
Nanomaterials 2022, 12, x 8 of 13
Sample code
Figure 6.
Figure 6. Macro
Macro performance
performance of
of SAC
SAC paste.
paste.
increased
3.3. rate of hydration in SAC and nucleation effect of GNPs, and providing for the
3.3. Heat
Heat of
of Hydration
Hydration
formation of hydration products. As the hydration reaction proceeded, the Ca2+ and Al3+
Figure 7a,b show the effect of GNPsGNPs on the hydration heat flow and2+cumulative heat
in theFigures
samples 7adecreased.
and b show the effect
After 12 h, of24 h and on48 the
h ofhydration
hydration,heat
theflow
Ca andion cumulative
concentra‐
of SAC.
heat of Adding GNPs shortened the induction period of SAC. The induction periods
tions in SAC.
G0 wereAdding 25.49GNPs
mg/L,shortened
19.48 mg/L, the and
induction periodand
15.07 mg/L, of SAC. The
the Ca induction periods
2+ concentrations in
of
of G0,
G0, G1,
G1, G2,
G2, and
and G3
G3 ended
ended at
at 57.3
57.3 min,
min, 48.6
48.6 min,
min, 54.6
54.6 min,
min, and 48
and 48 min,
min, respectively,
respectively,
G2 were 22.41 mg/L,16.95 mg/L, and 12.26 mg/L, respectively. The concentration of Ca2+
indicating
indicating that the
the acceleration
that from acceleration of the hydration of of SAC and
and an
an increase in
in the
the cumulative
ions decreased 4 h to 12 h of
due the
tohydration
AFt membrane SACrupturing increase
due to osmotic cumulative
pressure
heat occurred
heatthe
occurred due to
due to the huge specific surface area of GNPs, which provided sites for
for the
and formation of the
AFt,huge specific surface
corresponding area
to the of GNPs,
second which provided
exothermic peak thatsites
appeared.the
nucleation
nucleation of hydration products. AsAsthe hydration reaction proceeded, the first exothermic
AFt and AHof hydration
3 filled products.
the channels as the the hydration
hydration reaction
proceeded, proceeded,
resulting in athe first
higher exother‐
concen‐
peak appeared,
mic peak appeared,corresponding to the formation of the AFt.AFt.
TheThe
firstfirst
exothermic peaks of
tration
G0, G1,of G2Caandions
2+ incorresponding
the G0 at
G3 appeared group to the formation
solution
75.9 min, 74.2than
min,in
ofthe
71.5
the
G2 group
min,
exothermic
solution.
and 72.1 min. The The Capeaks
2+ ion
formation
of G0, G1, G2 and
concentration G3 appeared
in each solution at 75.9 min,
decreased 74.2 min, 71.512–48
min, and
h. 72.1 min. The formation
of hydration products was closely relatedslowly within
to the ion concentration in the solution.
of hydration products was closely related to the ion concentration in the solution.
(a) Figure 8 shows the ion concentration (b) trend of Ca2+ and Al3+ after hydration samples
0.035 0.035
G0 and G2, measured by ICP. After 0.5 h, 1 h, 2 h, and 4 h of hydration, the Ca2+ ion con‐
0.030 G0 G0
centrations in the solutionG1 of the200
G0 groupG1 were 89.41 mg/L, 68.41 mg/L, 53.47 mg/L, and
0.030 0.025
Heat flow(W/g)

0.020
43.52 mg/L, respectively. G2 G2
The Ca2+ concentrations in the solution of the G2 group were
Cumulative heat(J/g)

G3 G3
0.025 0.015 91.37 mg/L, 70.94 mg/L, 55.75 mg/L, and 46.08 mg/L, respectively. The concentration of
150
Heat flow(W/g)

0.010
Ca2+ in the G2 group was observed to be significantly higher than in the G0 group. The
100
0.020 0.005
0.8 Al3+ concentration curve and the Ca2+ concentration curve have similar trends.
1.0 1.2 1.4 1.6 1.8 2.0
Cumulative heat(J/g)

Time(h)

In the SAC hydrolysis stage,100

0.004 C4A3Š hydrolyzed and released Ca2+. Due to the adsorp‐
0.015
tion effect of GNPs, GNPs absorbed the Ca2+, and the 50
Ca2+ concentration around C4A3Š
Heat flow(W/g)

0.003

0.010 decreased, which promoted the hydrolysis of C4A3Š and released more Ca2+, leading to an
0.002 50
0.005 0
0.001 1 2 3 4 5
6 8 10
Time(h) Time(h)
0.000
0 10 20 30 40 0 10 20 30 40
Time(h) Time(h)
Figure
Figure 7.
7. (a,b)
(a,b) Isothermal
Isothermal calorimetry
calorimetry results.
results.

Figure 8 shows 2+ 3+
G0the ion concentration trend of Ca and Al after hydration samples
100 G2, measured by
G0 and
40 G0
ICP. After 0.5 h, 1 h, 2 h, and
G2 4 h of hydration, the Ca
2+ ion
G2
tion of Ca2+(mg/L)

oncentration of Al3+(mg/L)

35
concentrations in the solution of the G0 group were 89.41 mg/L, 68.41 mg/L, 53.47 mg/L,
and 43.52
80 mg/L, 30
respectively. The Ca2+ concentrations in the solution of the G2 group were
25

20
60 15

10
 0.020 0.8 1.0 1.2 1.4 1.6 1.8 2.0

Heat flow

Cumulative heat(J/g)
Cumulative
Time(h)
0.004

0.015 100
50

Heat flow(W/g)
0.003

0.010
0.002 50
Nanomaterials 2022, 12, 2708 8 of 12
0.005 0
0.001 1 2 3 4 5
6 8 10
Time(h) Time(h)
0.000
0 10 20 30 40 0 10 20 30 40
91.37 mg/L, 70.94 mg/L, 55.75 mg/L, and 46.08 mg/L, respectively. The concentration of
Time(h) Time(h)
Ca2+ in the G2 group was observed to be significantly higher than in the G0 group. The
Al3+ concentration
Figure curvecalorimetry
7. (a,b) Isothermal and the Ca 2+ concentration curve have similar trends.
results.

G0
100 40 G0
G2
Concentration of Ca2+(mg/L)
G2

Concentration of Al3+(mg/L)
35

30
80
25

20
60 15

10
40 5
0 10 20 30 40 50
Time(h)
20

0
0 10 20 30 40 50
Time(h)
8. ICP results of sulfoaluminate
Figure 8. sulfoaluminate cement
cement paste.
paste.

In theand
3.4. XRD SAC hydrolysis
TG‐DTG stage, C4 A3 Š hydrolyzed and released Ca2+ . Due to the adsorp-
Analysis
tion effect
Figureof9GNPs,
showsGNPs absorbed
the samples’ XRD Ca2+ , and
thepatterns of the
AFt,Ca
2+
AH3concentration
, C4A3Š, C2S,2+around
and C4 A3It
gypsum. Š
decreased, which promoted the hydrolysis of C A
4 3
was found that after adding GNPs, the peak positions Š and released more Ca , leading to
of different samples were the same, an
increased
and no new rate of hydration
diffraction in appeared,
peaks SAC and nucleation
but the peak effect of GNPs,
intensities anddifferent.
were providing forpeak
The the
formation of hydration products. As the hydration reaction proceeded, the Ca2+ and Al3+ in
intensity of the AFt in the GNPs group is higher than that of the G0 group, indicating that
the samples decreased. After 12 h, 24 h and 48 h of hydration, the Ca2+ ion concentrations
GNPs promoted the hydration of SAC, which is consistent with other studies that found
in G0 were 25.49 mg/L, 19.48 mg/L, and 15.07 mg/L, and the Ca2+ concentrations in G2
were 22.41 mg/L,16.95 mg/L, and 12.26 mg/L, respectively. The concentration of Ca2+ ions
decreased from 4 h to 12 h due to AFt membrane rupturing due to osmotic pressure and
the formation of AFt, corresponding to the second exothermic peak that appeared. AFt
and AH3 filled the channels as the hydration proceeded, resulting in a higher concentra-
tion of Ca2+ ions in the G0 group solution than in the G2 group solution. The Ca2+ ion
concentration in each solution decreased slowly within 12–48 h.

3.4. XRD and TG-DTG Analysis

Figure 9 shows the samples’ XRD patterns of AFt, AH3 , C4 A3 Š, C2 S, and gypsum. It
was found that after adding GNPs, the peak positions of different samples were the same,
and no new diffraction peaks appeared, but the peak intensities were different. The peak
intensity of the AFt in the GNPs group is higher than that of the G0 group, indicating
that GNPs promoted the hydration of SAC, which is consistent with other studies that
found that the hydration mechanism of GNPs promotes OPC because the nucleation effect
of GNPs promoted the hydration reaction. Still, as no chemical reaction occurs, no new
hydration products are generated [31].
As shown in Figure 10, there were four weight loss peaks. The first weight loss
peak appeared at 100–150 ◦ C, corresponding to the dehydration and decomposition of
AFt [32,33], and the second peak occurred at 150–200 ◦ C, corresponding to the decom-
position of gypsum [32,33]. The third weight loss peak appeared at 210–270 ◦ C [32,33],
corresponding to the decomposition of AH3 . The fourth weight loss peak occurred at
650–800 ◦ C, corresponding to the decomposition of calcium carbonate. In the temperature
range of 450–510 ◦ C, there was no weight loss peak, indicating that CH (calcium hydroxide)
was not generated, which is consistent with the analysis results of XRD. After adding GNPs,
 appeared
appeared at at 100–150
100–150 °C,°C, corresponding
corresponding to to the
the dehydration
dehydration and and decomposition
decomposition of of AFt
AFt [32–
[32–
33],
33], and
and the
the second
second peak
peak occurred
occurred at at 150–200
150–200 °C,°C, corresponding
corresponding to to the
the decomposition
decomposition of of
gypsum
gypsum [32–33].
[32–33]. The
The third
third weight
weight loss
loss peak
peak appeared
appeared at at 210–270
210–270 °C°C [32–33],
[32–33], correspond‐
correspond‐
ing
ing to
to the
the decomposition
decomposition of of AH
AH33.. The
The fourth
fourth weight
weight loss
loss peak
peak occurred
occurred atat 650–800
650–800 °C,
°C,
Nanomaterials 2022, 12, 2708 corresponding to the decomposition of calcium carbonate. In the
corresponding to the decomposition of calcium carbonate. In the temperature range temperature range of
of
9 of 12
450–510
450–510 °C,°C, there
there was
was nono weight
weight loss
loss peak,
peak, indicating
indicating that
that CH
CH (calcium
(calcium hydroxide)
hydroxide) waswas
not
not generated,
generated, which
which is is consistent
consistent with
with the
the analysis
analysis results
results of
of XRD.
XRD. After
After adding
adding GNPs,
GNPs,
the
the weight
weight loss
loss of
of AFt
AFt was
was larger
larger than
than that
that of
of the
the G0
G0 group,
group, and
and the
the TG‐DTG
TG‐DTG andand XRD
XRD
the weight loss of AFt was larger than that of the G0 group, and the TG-DTG and XRD
analysis
analysis results
results are
are consistent.
consistent. GNPs
GNPs promoted
promoted the the hydration
hydration ofof SAC
SAC andand generated
generated more
more
analysis results are consistent. GNPs promoted the hydration of SAC and generated more
hydration
hydration products.
products.
hydration products.
E:AFt
E:AFt G
G
Y:Ye'elimite
Y:Ye'elimite ZZ
A:AH
A:AH33
G:Gypsum
G:Gypsum E E Y
Y
C:Calcite
C:Calcite
Z:ZnO
Z:ZnO EE EE
B:C22SS
B:C EE BB E
G B EY
CCG B Y
EE Y
Y Y
Y
G3
G3 G
G A
A G
G

G2
G2

G1
G1

G0
G0

88 10
10 12
12 14
14 16
16 18
18 20
20 22
22 24
24 26
26 28
28 30
30 32
32 34
34
2θ
2θ (degree)
(degree)
Figure 9.
Figure9.
Figure XRD
9.XRD analysis
XRDanalysis of
analysisof sulfoaluminate
ofsulfoaluminate cement
sulfoaluminatecement paste.
cementpaste.
paste.

0.0000
0.0000
0.004
0.004
100
100 G0
G0
G1
G1
0.003
0.003
DTG (%/℃)
DTG (%/℃)

95
95 G2
G2
-0.0005 G3
G3
90
-0.0005
90 0.002
0.002
85
85
DTG (%/℃)

200
200 220
220 240
240 260
260 280
280

0.001
Temperature
Temperature(℃)
0.001
(℃)
TG (%)

80
80
75 0.000
0.000
75 AH
AH33
0.0010
0.0010

70
70 -0.001
0.0005

-0.001
0.0005
0.0000
0.0000
DTG (%/℃)
DTG (%/℃)

-0.0005
-0.0005
CaCO
CaCO33
65
65 -0.0010
-0.0010
-0.0015
-0.0015
-0.0020
-0.0020
-0.002
-0.002
60
60 -0.0025
-0.0025
-0.0030
-0.0030

AFt
AFt
8080 100
100
-0.003
-0.003
120
120 140
140 160160 180
180 200
200

55
55
Temperature
Temperature(℃)
(℃)

100
100 200
200 300
300 400
400 500
500 600
600 700
700 800
800 900
900 1000
1000
Temperature
Temperature (℃)
(℃)
Figure
Figure 10.
Figure10. TG−DTG
10.TG −DTGanalysis
TG−DTG analysis of
analysis of sulfoaluminate
of sulfoaluminate cement
sulfoaluminate cement paste.
cement paste.
paste.

3.5.
3.5.Reinforcing
3.5. ReinforcingMechanism
Reinforcing Mechanism
Mechanism
Figure 11 shows the morphology of GNPs in cement-based materials. GNPs are deeply
embedded in the cement matrix and are bent and curled. The matrix form a tight bond,
which is beneficial to improving the mechanical properties of cement-based materials,
as shown in Figure 11a, b. GNPs would be pulled out from the cement matrix when an
external force loads the graphene. As shown in Figure 11c, when the GNPs are extracted,
GNPs would consume part of the energy and improve the bearing capacity of the matrix.
It can be seen that the hydration product AFt is attached to the surface of pulled-out GNPs,
indicating that the hydration product and GNPs are tightly connected, further improving
the bonding strength between GNPs and the substrate. When the content of GNPs in the
cement matrix is too high, GNPs will agglomerate. It can be seen from Figure 11d that the
GNPs form parallel planes, and voids form between adjacent GNPs, which are not filled
Nanomaterials 2022, 12, 2708 10 of 12

by hydration products. When the load is applied, the parallel planes formed by GNPs are
weak, and the GNPs are easily pulled out, thus reducing the mechanical properties. The
two-dimensional stacked lamellar structure of GNPs embedded in the cement matrix can
bridge and delay the development of microcracks and improve the mechanical properties
of the cement matrix, as shown in Figure 11e. When the cracks were filled with GNPs,
some were blocked, and some developed to both ends along the GNPs, which significantly
Nanomaterials 2022, 12, x 11 of 13
increased the cracks’ development paths and improved the matrix’s bearing capacity, as
shown in Figure 11f.

Figure11.
Figure 11. Morphology
Morphology of
of GNPs
GNPs in
insulfoaluminate
sulfoaluminatecement
cementpaste.
paste.

4. Conclusions
From the analysis of hydration heat, ICP, XRD, TG, and SEM, and the changes in
macroscopic
This paper mechanical properties,
characterized we can determine
the dispersion effect ofthe mechanism
GNPs, studiedofthe GNPs in of
effect promot-
GNPs
ing SAC hydration, enhancement, and crack inhibition. In the SAC
after dispersion on the hydration process and hydration products of SAC, and revealed hydrolysis stage, C4 A3 Š
hydrolyzed
the mechanism and of released Ca2+ . Duehydration
GNP‐enhanced to the adsorption
of SAC. Dueeffecttoof GNPs,
the GNPs effect
adsorption absorbedand the
nu‐
Ca 2+ ions,effect
and the 2+
Ca concentration around C4 A3 ŠCa
decreased, which
cleation of GNPs, GNPs were able to absorb 2+, decreasing thewould promote the
Ca2+ concentration
hydrolysis
around C4A of3Š,C4which
A3 Š and release more
subsequently Ca2+ , thus
promoted theaccelerating
hydrolysis of theChydration of SAC, the
4A3Š and release more
nucleation effect of GNPs, and provide sites for the formation of hydration
Ca , accelerating the hydration of SAC and providing sites for the formation of hydration
2+ products. GNPs
promoted the hydration of SAC and formed more AFt and AH 3 .
products. During the hydration process, sufficient ion exchange promoted the hydrationThe generated hydration
products
of SAC and fill the poresmore
formed of the matrix. They
hydration are closely
products, connected
including AFt and with
AHthe GNPs to form a
3. These hydration
whole,
products filled the pores of the matrix. They are closely connected with thethe
which improves the cement matrix’s mechanical properties. When loadtoacted
GNPs form
on
a whole, which improves the cement matrix’s mechanical properties. When the load and
the matrix, GNPs enhanced matrix performance by filling, bridging, deflecting, acts
pulling out.
on the matrix, the GNPs enhanced the performance of the matrix by filling, bridging, de‐
flecting, and pulling out. This research proposed a new type of low‐carbon ecological ce‐
ment composite, which will help the construction industry to save energy, reduce CO2
emissions, and achieve sustainable development. With the discovery and development of
the construction industry, GNPs have excellent thermal, mechanical, and electrical prop‐
erties and can be used in cement to develop intelligent pressure‐sensitive materials, elec‐
Nanomaterials 2022, 12, 2708 11 of 12

4. Conclusions
This paper characterized the dispersion effect of GNPs, studied the effect of GNPs
after dispersion on the hydration process and hydration products of SAC, and revealed
the mechanism of GNP-enhanced hydration of SAC. Due to the adsorption effect and
nucleation effect of GNPs, GNPs were able to absorb Ca2+ , decreasing the Ca2+ concen-
tration around C4 A3 Š, which subsequently promoted the hydrolysis of C4 A3 Š and release
more Ca2+ , accelerating the hydration of SAC and providing sites for the formation of
hydration products. During the hydration process, sufficient ion exchange promoted the
hydration of SAC and formed more hydration products, including AFt and AH3 . These
hydration products filled the pores of the matrix. They are closely connected with the
GNPs to form a whole, which improves the cement matrix’s mechanical properties. When
the load acts on the matrix, the GNPs enhanced the performance of the matrix by filling,
bridging, deflecting, and pulling out. This research proposed a new type of low-carbon
ecological cement composite, which will help the construction industry to save energy,
reduce CO2 emissions, and achieve sustainable development. With the discovery and
development of the construction industry, GNPs have excellent thermal, mechanical, and
electrical properties and can be used in cement to develop intelligent pressure-sensitive ma-
terials, electromagnetic wave-absorbing materials, and electromagnetic shielding materials.
We believe that, in the future, cement-based smart, multifunctional materials developed
with carbon-based materials will become the focus of engineering applications and have
broad market prospects.

Author Contributions: Conceptualization, K.C. and J.C.; Formal analysis, K.C., J.C. and M.M.S.S.;
Funding acquisition, M.M.S.S. and J.H.; Supervision, J.C. and J.H.; Writing—review and editing,
M.M.S.S., J.C. and J.H., Writing—original draft, K.C. All authors have read and agreed to the published
version of the manuscript.
Funding: This research is partially funded by the Ministry of Science and Higher Education of the
Russian Federation under the strategic academic leadership program ‘Priority 2030’ (Agreement
075-15-2021-1333 dated 30.09.2021).
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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