Electrical Piezoresistive and Electromagnetic Prop

nanomaterials
Review
Electrical, Piezoresistive and Electromagnetic Properties
of Graphene Reinforced Cement Composites: A Review
Shengchang Mu, Jianguang Yue, Yu Wang and Chuang Feng *
College of Civil Engineering, Nanjing Tech University, Nanjing 211800, China;

[email protected] (S.M.); [email protected] (J.Y.); [email protected] (Y.W.)
* Correspondence: [email protected]
Abstract: Due to their excellent combination of mechanical and physical properties, graphene and
its derivatives as reinforcements have been drawing tremendous attention to the development of
high-performance and multifunctional cement-based composites. This paper is mainly focused on
reviewing existing studies on the three material properties (electrical, piezoresistive and electromag-
netic) correlated to the multifunction of graphene reinforced cement composite materials (GRCCMs).
Graphene fillers have demonstrated better reinforcing effects on the three material properties in-
volved when compared to the other fillers, such as carbon fiber (CF), carbon nanotube (CNT) and
glass fiber (GF). This can be attributed to the large specific surface area of graphene fillers, leading to
improved hydration process, microstructures and interactions between the fillers and the cement
matrix in the composites. Therefore, studies on using some widely adopted methods/techniques
to characterize and investigate the hydration and microstructures of GRCCMs are reviewed and
discussed. Since the types of graphene fillers and cement matrices and the preparation methods affect
the filler dispersion and material properties, studies on these aspects are also briefly summarized
and discussed. Based on the review, some challenges and research gaps for future research are
Citation: Mu, S.; Yue, J.; Wang, Y.; identified. This review is envisaged to provide a comprehensive literature review and more insightful
Feng, C. Electrical, Piezoresistive and perspectives for research on developing multifunctional GRCCMs.
Electromagnetic Properties of
Graphene Reinforced Cement Keywords: graphene; cement composite; electrical conductivity; piezoresistivity; electromagnetic shielding
Composites: A Review. Nanomaterials
2021, 11, 3220. https://doi.org/
10.3390/nano11123220
1. Introduction
Academic Editor: Carlo Mariani
Cement composite materials (CCMs) are the most commonly used building materials
in civil engineering because of their easy processability, availability, low cost, and excellent
Received: 27 October 2021
Accepted: 25 November 2021
compressive strength [1]. However, CCMs also have drawbacks, such as low tensile strength,
Published: 27 November 2021
brittleness, and susceptibility to a harsh environment [2–4]. These drawbacks could lead to
inferior durability and high cost for maintenance, which have raised great concern in civil
Publisher’s Note: MDPI stays neutral
engineering. One of the attempts to solve the above-mentioned issues is to add reinforcements
with regard to jurisdictional claims in
into the traditional CCMs. Various fillers have been used as reinforcements for CCMs, including
published maps and institutional affil- carbon fiber (CF) [5–8], glass fiber (GF) [9,10], carbon black (CB) [11,12], and carbon nanotube
iations. (CNT) [13–15]. Recently, graphene and its derivatives have been attracting great attention as
reinforcing fillers for developing CCMs. Such interest stems from the extraordinary mechanical
and physical properties of these nano fillers. The Young’s modulus, thermal conductivity, and
electrical conductivity of the graphene fillers can reach up to 1 TPa, 5000 W·m−1 ·K−1 and
Copyright: © 2021 by the authors.
6000 S·cm−1, respectively [16–18]. Research has demonstrated that the addition of graphene
Licensee MDPI, Basel, Switzerland.
fillers into cement matrices can remarkably improve both the physical and mechanical properties
This article is an open access article
of the CCMs. For example, Najafishad et al. [19] found the compressive strength of CCMs was
distributed under the terms and enhanced by 41% when 0.1 wt% graphene oxide (GO) was added. Pisello et al. [20] compared
conditions of the Creative Commons four nano-inclusions and found that graphene nanoplatelet (GNP) was the most effective
Attribution (CC BY) license (https:// nano-inclusion to improve the thermal conductivity of CCMs, enhancing the value from 0.78
creativecommons.org/licenses/by/ W·m−1 ·K−1 to 1.14 W·m−1 ·K−1. There are many other works on the mechanical and thermal
4.0/). properties of graphene reinforced cement composite materials (GRCCMs) [21–32].
Nanomaterials 2021, 11, 3220. https://doi.org/10.3390/nano11123220 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2021, 11, 3220 2 of 32
nano-inclusions and found that graphene nanoplatelet (GNP) was the most effective
Nanomaterials 2021, 11, 3220 nano-inclusion to improve the thermal conductivity of CCMs, enhancing the value 2from of 31
0.78 W·m–1·K–1 to 1.14 W·m–1·K–1. There are many other works on the mechanical and ther-
mal properties of graphene reinforced cement composite materials (GRCCMs) [21–32].
In addition to mechanical properties, existing studies also demonstrated that
GRCCMsIn addition to mechanicalexcellent
have considerably properties, existing
physical studies also
properties, demonstrated
which stem fromthat
theGRCCMs
inherent
have considerably
attributes excellentfillers.
of the graphene physical properties,
Utilizing thesewhich stem
physical from the inherent
properties, attributes
these CCMs of
infused
the graphene fillers. Utilizing these physical properties, these CCMs infused with graphene
with graphene filler can be served as sensors and electromagnetic shielding materials for
filler can be served as sensors and electromagnetic shielding materials for structural health
structural health monitoring and corrosion protection [33–35]. There have been a few pa-
monitoring and corrosion protection [33–35]. There have been a few papers summarizing
pers summarizing the work on GRCCMs, particularly on mechanical properties. How-
the work on GRCCMs, particularly on mechanical properties. However, relatively less
ever, relatively less work has been found on comprehensive surveys of physical proper-
work has been found on comprehensive surveys of physical properties. Therefore, in
ties. Therefore, in this paper, we are going to review the studies that are related to three
this paper, we are going to review the studies that are related to three properties, i.e.,
properties, i.e., electrical conductivity/resistivity, piezoresistivity, and electromagnetic
electrical conductivity/resistivity, piezoresistivity, and electromagnetic shielding. Firstly,
shielding. Firstly, we review the materials used and the preparation methods for
we review the materials used and the preparation methods for GRCCMs. The work on
GRCCMs. The work on characterizing the GRCCMs by some widely used methods/facil-
characterizing the GRCCMs by some widely used methods/facilities is introduced. Then
ities is introduced. Then both the theoretical and experimental work on the three proper-
both the theoretical and experimental work on the three properties as mentioned are
ties as mentioned are presented and discussed.
presented and discussed.
2.
2. Graphene-Reinforced
Graphene-Reinforced Cement
Cement Composite Materials
Composite Materials
The
The graphene
graphene fillers, cement matrices,
fillers, cement matrices, and
and the
the preparation
preparation methods
methods of
of GRCCMs
GRCCMs are
are
introduced and discussed, respectively, in this section.
introduced and discussed, respectively, in this section.
2.1. Graphene Filler

are different
There are differentforms
formsandandtypes
typesof of graphene
graphene andand its derivatives
its derivatives [36,37].
[36,37]. As
As rein-
reinforcements in a matrix, various graphene fillers have been used to
forcements in a matrix, various graphene fillers have been used to develop high-perfor-develop high-
performance and multifunctional
mance and multifunctional CCMs.CCMs.
In the In the following,
following, themain
the four fourtypes
main of
types of graphene
graphene fillers
fillers
as as shown
shown in Figure
in Figure 1 are introduced
1 are introduced and discussed.
and discussed.
1. Four
Figure 1. Fourtypes
typesofofgraphene
graphenefillers forfor
fillers GRCCMs.
GRCCMs.(a) Graphene, (b) Graphene
(a) Graphene, Oxide,
(b) Graphene (c) Reduced
Oxide, (c) Re-
duced Graphene Oxide. Reprinted with permission from Ref. [38]. Copyright 2021 Elsevier.
Graphene Oxide. Reprinted with permission from Ref. [38]. Copyright 2021 Elsevier. (d) Graphene (d) Gra-
phene Nanoplatelets. Reprinted with permission from Ref. [39]. Copyright 2021
Nanoplatelets. Reprinted with permission from Ref. [39]. Copyright 2021 Elsevier. Elsevier.
(a) Graphene
Graphene
As the reinforcing filler in a matrix, it should
should be noted that graphene here normally
refers to
to the
thesheet
sheetwith
witha afew layers
few instead
layers of monolayer
instead graphene
of monolayer thatthat
graphene exists on a on
exists substrate
a sub-
only. It can be manufactured by mechanical, liquid-phase, and electrochemical exfoliation
strate only. It can be manufactured by mechanical, liquid-phase, and electrochemical ex-
and chemical
foliation and vapor deposition
chemical [40,41]. Extensive
vapor deposition [40,41]. work has been
Extensive carried
work out to
has been enhance
carried outthe
to
material properties of CCMs by utilizing graphene [42–47]. Ho et al. [42] observed that the
incorporation of 0.07 wt% pristine graphene increased the tensile strength of the CCMs by
26.9% at 28 days. Figure 2 shows the variation of the electrical conductivity of GRCCMs
with graphene (less than three layers) concentration [43]. The electrical conductivity of the
GRCCMs underwent percolation behaviour and reached a value larger than 10−3 S/cm.
enhance the material properties of CCMs by utilizing graphene [42–47]. Ho et al. [42] ob-
served that the incorporation of 0.07 wt% pristine graphene increased the tensile strength
of the CCMs by 26.9% at 28 days. Figure 2 shows the variation of the electrical conductiv-
Nanomaterials 2021, 11, 3220
ity of GRCCMs with graphene (less than three layers) concentration [43]. The electrical
3 of 31
conductivity of the GRCCMs underwent percolation behaviour and reached a value larger
than 10–3 S/cm.
2. Variation
Figure 2. Variation of
of electrical
electrical conductivity
conductivity of
of GRCCMs
GRCCMs with
withgraphene
grapheneconcentration.
concentration. Reprinted
Reprinted
permission from
with permission from Ref.
Ref. [43].
[43]. Copyright
Copyright 2020
2020 Thmas
Thmas Telford
TelfordLtd.
Ltd.
Despite graphene’s
graphene’sattractive
attractiveattributes,
attributes,it it
hashas
oneone obvious
obvious disadvantage—a
disadvantage—a low low
dis-
dispersibility—which
persibility—which cancan leadlead to agglomeration
to agglomeration inmatrix.
in the the matrix. Moreover,
Moreover, the current
the current meth-
methods arechallenging
ods are still still challenging to massively
to massively produce
produce high-quality
high-quality graphene
graphene with with moderate
moderate cost.
cost. Such a disadvantage gives rise to the other derivatives, including GO,
Such a disadvantage gives rise to the other derivatives, including GO, reduced graphene reduced
graphene oxide
oxide (rGO), and(rGO),
GNP.and GNP.
(b) GrapheneOxide
(b) Graphene Oxide
GO
GO isis aa derivative
derivative of
of graphene
graphene with
with layer
layer spacing
spacing from
from 0.7
0.7 to
to 1.2
1.2 nm.
nm. The
The synthesis
synthesis
of GO can be mainly achieved by treating graphite with oxidants and potassium
of GO can be mainly achieved by treating graphite with oxidants and potassium perman- perman-
ganate followed by exfoliation. The surface of GO contains a large number of functional
ganate followed by exfoliation. The surface of GO contains a large number of functional
groups, including carbonyl, epoxide, hydroxyl, and carboxyl. Because of the functional
groups, including carbonyl, epoxide, hydroxyl, and carboxyl. Because of the functional
groups, GO is hydrophilic and highly dispersible in organic solvents. This enables GOs to
groups, GO is hydrophilic and highly dispersible in organic solvents. This enables GOs to
be the preferred reinforcing fillers for CCMs. Yu and Wu’s [48] experiments demonstrated
be the preferred reinforcing fillers for CCMs. Yu and Wu’s [48] experiments demonstrated
that the addition of GO significantly increased the durability and mechanical properties
that the addition of GO significantly increased the durability and mechanical properties
of CCMs. Zhang et al.’s [49] molecular dynamic (MD) simulation showed that the incor-
of CCMs. Zhang et al.’s [49] molecular dynamic (MD) simulation showed that the incor-
poration of GO weakened the effects of moisture concentration on CCMs. Fan et al. [50]
poration of GO weakened the effects of moisture concentration on CCMs. Fan et al. [50]
executed repeated simulations by MDs and found that GO and cement matrix had a strong
executed repeated simulations by MDs and found that GO and cement matrix had a
interfacial bond strength. Wang et al. [51] reported that GO had a considerable capacity for
Nanomaterials 2021, 11, 3220 strong interfacial bond strength. Wang et al. [51] reported that GO had a considerable
absorption on the cement surface due to the chemical reaction of the carboxyl groups4atofthe32
capacity for absorption on the cement surface due to the chemical reaction of the carboxyl
edge of GO filler (as shown in Figure 3).
groups at the edge of GO filler (as shown in Figure 3).
Although GO demonstrates some advantages, it also has disadvantages. It contains
defects and its mechanical properties are considerably inferior to graphene. Moreover, GO
has a much lower electrical conductivity and electron mobility, limiting its application as
reinforcements in developing multifunctional CCMs.
Figure 3.
Figure Chemical adsorption
3. Chemical adsorption reaction
reactionschematic
schematicofofGOGOononcement
cementsurface. (a)(a)
surface. Adsorption of GO
Adsorption on
of GO
on
thethe cement
cement surface.
surface. (b)(b)
TheThe substitutionreaction
substitution reactionofofGO
GOininthe
theadsorption
adsorptionsystem.
system. Reprinted with
permission
permission from
from Ref.
Ref. [51].
[51]. Copyright
Copyright 2016
2016 RSC
RSC Publishing.
Publishing.
(c) Reduced Graphene Oxide

rGO is another valuable derivative of graphene. It can be manufactured by removing
part of the functional groups of GO. Several methods, including thermal, chemical, and
photo-thermal reduction, can be utilized to manufacture rGO. The thermal reduction pro-
Figure 3. Chemical adsorption reaction schematic of GO on cement surface. (a) Adsorption of GO

on theAlthough GO demonstrates
cement surface. somereaction
(b) The substitution advantages, it also
of GO in has disadvantages.
the adsorption It contains
system. Reprinted with
defects and
permission its mechanical
from properties
Ref. [51]. Copyright 2016are considerably
RSC Publishing. inferior to graphene. Moreover, GO
has a much lower electrical conductivity and electron mobility, limiting its application as
reinforcements
(c) in developing
Reduced Graphene Oxide multifunctional CCMs.
(c) rGOReduced Graphene
is another Oxide
valuable derivative of graphene. It can be manufactured by removing
part of the functional groups of GO. Several
rGO is another valuable derivative methods,
of graphene. including
It can thermal, chemical,
be manufactured and
by removing
photo-thermal reduction,
part of the functional groupscanofbe
GO.utilized
Severaltomethods,
manufacture rGO.thermal,
including The thermal reduction
chemical, pro-
and photo-
cess takes
thermal place at can
reduction, a temperature
be utilized tobetween 300 °C–2000
manufacture rGO. The °Cthermal
in an environment with inert
reduction process takes
air or aatreduced
place atmosphere.
a temperature betweenFor ◦ C–2000 reduction,
300chemical ◦ C in an environment
inorganic agents, such
with inert airasorhydroxyl-
a reduced
amine or phenyl hydrazine hydrate, are normally used. The photo-thermal
atmosphere. For chemical reduction, inorganic agents, such as hydroxylamine or phenyl reduction can
be completed by a laser beam with a wavelength under 390 nm. After
hydrazine hydrate, are normally used. The photo-thermal reduction can be completed by a reduction, rGO can
possess
laser beamcomparable mechanical
with a wavelength and electrical
under properties
390 nm. After such rGO
reduction, as graphene [52].comparable
can possess Phrompet
et al. [31] demonstrated
mechanical and electricalthat the incorporation
properties of rGO
such as graphene effectively
[52]. Phrompetimproved
et al. [31] the mechani-
demonstrated
cal,
thatthermal, and dielectric
the incorporation of rGOproperties of CCMs.
effectively improved Zhang et al. [53] simply
the mechanical, mixed
thermal, and rGO into
dielectric
cement
propertiesandofthe electromagnetic
CCMs. Zhang et al. [53]shielding
simply effectiveness
mixed rGO into was significantly
cement improved. As
and the electromagnetic
shown in Figure
shielding 4, the was
effectiveness experimental
significantlysample with 1.0
improved. As wt%shownrGO added 4,
in Figure hasthea experimental
value of 16–
sample
21 with 1.0
dB (GC1) for wt% rGO added has
electromagnetic a valueeffectiveness,
shielding of 16–21 dB (GC1) for electromagnetic
an enhancement of 30%shielding
to 45%
effectiveness,
compared an enhancement
to the sample without of 30%
rGOto(GC0).
45% compared to the sample without rGO (GC0).
Figure 4. Comparison
Figure Comparisonofof shielding effectiveness
shielding of reinforced
effectiveness CCMs CCMs
of reinforced with and without
with and rGO. Reprinted
without rGO.
Reprinted from Ref. [53].
from Ref. [53].
Comparedto
Compared toGO,
GO,rGO
rGOhas
hasfavorable
favorableattributes.
attributes.However,
However,rGO rGOalsoalsohas
hassome
somedraw-
draw-
backs.ItsIts
backs. dispersibility
dispersibility in CCMs
in CCMs decreases
decreases compared
compared to GO todue
GOtodue to its hydrophobic
its hydrophobic attrib-
attributes.
utes. DespiteDespite the decreased
the decreased dispersibility,
dispersibility, rGO isrGO is still regarded
still regarded as a promising
as a promising rein-
reinforcing
forcing filler for its excellent mechanical and physical properties as well as its low cost and
availability for scalable preparation.
(d) Graphene Nanoplatelet
GNP is a reinforcing filler with platelet-shaped graphene sheets stacked. It can be
obtained by using natural graphite via methods such as thermal shock, chemical exfoliation,
plasma reactor or shear force. GNP possesses competent attributes such as lightweight,
high specific surface, low density, electric and thermal conductance, excellent mechanical
properties, lower cost, etc. Zohhadi et al. [54] and Zhu et al. [55] manufactured CCMs by
using GNP as reinforcements. Their experimental results indicated that GNP improved the
hydration process and generated more hydration products. Wang et al. [56] found that both
the flexural and compressive strengths were significantly enhanced when GNP was added.
Compared to the plain sample, the mechanical properties of reinforced CCM samples
at 0.05 wt% GNPs showed the most improved results, with flexural and compressive
strengths being enhanced by 27.4 and 4.3%, respectively, after 7 days of curing, and by 3.7%
and 25.2%, respectively, after 28 days of curing.
2.2. Cement Matrix

In the following, different cement matrices in developing GRCCMs are introduced
and discussed.
(a) Ordinary Portland Cement
Ordinary Portland Cement (OPC) is a water-hardened gel material, mixed with
blended materials and an appropriate amount of gypsum. The amount of the blended
materials does not exceed 15%. OPC has been extensively used as matrix to develop
GRCCMs. Gong et al. [57] dispersed GO in OPC and found that the addition of 0.03 wt%
GO increased the strength of CCMs by more than 40%. Ho et al. [42] used electrochemically
prepared graphene as reinforcements and found that the flexural and compressive strength
were enhanced by 26.9% and 34.3%, respectively, when 0.07 wt% graphene was dispersed.
Li et al. [58] carried out experiments on the influence of GO on the early hydration process
and mechanical properties of OPC pastes. The results showed that the strength of the GO
reinforced cement paste was significantly enhanced, and the hydration rate was accelerated.
(b) Portland Pozzolana Cement (PPC)
PPC is a mix of OPC, gypsum, and Pozzolanic materials in a certain proportion. Slag
and fly ash are usually added into OPC to develop PPC. Compared to OPC, PPC generates
less hydration heat at a lower rate. It also has a low permeability. Zhu et al. [59,60] studied
the effects of GO and GNP on the performances of slag PPC composites and evidenced that
the fillers accelerated the hydration degree. Chintalapudi et al. [32] dispersed GO in fly ash
PPC and found dense hydrated crystals formed by GO, which improved the compressive
strength of the CCMs. Wang et al. [61] added GO into fly ash PPC and investigated the
rheological properties. Figure 5 shows the mechanisms of the fly ash effect on the rheology
of the reinforcement CCMs. The mixing of fly ash PPC and GO improved the workability of
the composites. Sharma and Arora [62] used fly ash PPC as the matrix and added graphene
as reinforcements. At a concentration of 0.05 vol% graphene, the flexural and compressive
strength were increased by 13% and 8%, respectively. Wang et al. [63] and Saafi et al. [64]
used GO and rGO, respectively, as reinforcements for fly ash PPC and found that both the
fillers accelerated the secondary hydration at a later stage and reduced the porosity.
Figure
Figure 5. Schematic
Schematic diagram
diagram ofof the
the formation
formation of flocculation structure. (a)
(a) Cement paste, (b) GO
reinforced
reinforced cement
cement paste;
paste; (c) GO reinforced cement paste with fly ash.
ash. Reprinted with permission
from
from Ref.
Ref. [61].
[61]. Copyright
Copyright 2017
2017 Elsevier.
Elsevier.
2.3. Preparation
Apart from of OPC
Graphene
andReinforced
PPC, otherComposites
types of cement matrices, including Magnesium
Phosphate Cement (MPC), sulphoaluminate cement
Due to van der Waals force, it is challenging (SAC),
to add and magnesium
graphene fillers intopotassium
a cement
matrix randomly and uniformly. Poor dispersion of these fillers may lead to the deterio-
ration of the material properties and limit their engineering application. Therefore, nu-
merous measures have been developed to enable better dispersion of graphene fillers in
cement matrix. These measures can be categorized into dry-mix dispersion and wet-mix
dispersion (as shown in Figure 6). Physical dispersion methods are usually used in both
Figure 5. Schematic diagram of the formation of flocculation structure. (a) Cement paste, (b) GO
reinforced
phosphatecement
cementpaste; (c) GOare
(MKPC), reinforced cement
also used paste with
as matrices to fly ash. Reprinted
develop with permission
high-performance and
from Ref. [61]. Copyright
multifunctional GRCCMs 2017[65–68].
Elsevier.
2.3. Preparation
2.3. Preparation of
of Graphene
Graphene Reinforced
Reinforced Composites
Composites
Due to van der
Due der Waals
Waalsforce,
force,ititisischallenging
challenging to to
add
addgraphene
graphene fillers intointo
fillers a cement ma-
a cement
trix randomly
matrix randomlyandand
uniformly. PoorPoor
uniformly. dispersion
dispersionof these fillers
of these maymay
fillers lead lead
to thetodeterioration
the deterio-
of the of
ration material properties
the material and limit
properties andtheirlimitengineering application.
their engineering Therefore,
application. numerous
Therefore, nu-
measures
merous have been
measures havedeveloped to enable
been developed to better
enabledispersion of graphene
better dispersion fillers infillers
of graphene cementin
matrix. matrix.
cement These measures can be categorized
These measures into dry-mix
can be categorized intodispersion and wet-mix
dry-mix dispersion anddispersion
wet-mix
(as shown in
dispersion (asFigure
shown6).inPhysical
Figure 6).dispersion
Physicalmethods
dispersion aremethods
usually used in both used
are usually dry-mix and
in both
wet-mix dispersion techniques. However, it is challenging to use a
dry-mix and wet-mix dispersion techniques. However, it is challenging to use a physical physical dispersion
method to disperse
dispersion method to graphene
dispersefillers at the fillers
graphene micro/nano
at the meter scale [26,69,70].
micro/nano meter scale Therefore, in
[26,69,70].
the wet-mix
Therefore, indispersion,
the wet-mix researchers
dispersion, combined
researchers physical with chemical
combined physical dispersion
with chemical methods
dis-
to better disperse graphene fillers in CCMs.
persion methods to better disperse graphene fillers in CCMs.
Figure 6.
Figure Mixing methods
6. Mixing methods forfor graphene
graphene fillers
fillers in cement matrix. Reprinted
Reprinted with permission
permission from
Ref.
Ref. [71].
[71]. Copyright
Copyright2018
2018 IOP
IOP Publishing.
Publishing.
2.3.1. Dry-Mix Dispersion

For the dry-mix method, graphene fillers and the other dry ingredients are mixed by
high-speed stirring to prepare a homogeneous mixture. Then water and the other liquid
ingredients are added for molding and hardening of the composites. Liu et al. [72,73] adopted
the dry-mix method to prepare GNP-reinforced CCMs. As shown in Figure 7, GNP and
sand were first mixed by high-speed mechanical stirring. The high-speed impact and friction
between GNPs and the sand enabled the fillers to be attached to the sand and dispersed with
fewer aggregates. Then cement, water and other admixtures were added subsequently and
mixed. Sartipi et al. [74] mixed GO with cement and then placed the mixture on the vibrator for
consolidation purposes, allowing 24 h for curing. Ghosh et al. [75] utilized a ball mill to have a
homogenous distribution of GNP in cement. Mixed raw materials were placed into a cylindrical
steel die for ball milling and then were compressed at 40 MPa to make it bulk and cured.
and friction between GNPs and the sand enabled the fillers to be attached to the sand and
dispersed with fewer aggregates. Then cement, water and other admixtures were added
subsequently and mixed. Sartipi et al. [74] mixed GO with cement and then placed the
mixture on the vibrator for consolidation purposes, allowing 24 h for curing. Ghosh et al.
[75] utilized a ball mill to have a homogenous distribution of GNP in cement. Mixed raw
materials were placed into a cylindrical steel die for ball milling and then were com-
pressed at 40 MPa to make it bulk and cured.
Figure7.
Figure Dry-mixdispersion
7. Dry-mix dispersionmethod
methodto
toprepare
prepareGNP
GNPreinforced
reinforcedCCMs.
CCMs.Reprinted
Reprintedfrom
fromRef.
Ref.[72].
[72].
Copyright2018
Copyright 2018Elsevier.
Elsevier.
The procedure
The procedure of of the
the dry-mix
dry-mix dispersion
dispersionmethod
methodisisasasfollowing:
following:(1)
(1)the
thedry
drymaterials,
materi-
such as graphene filler, cement, and sand, etc., are mixed by a mechanical
als, such as graphene filler, cement, and sand, etc., are mixed by a mechanical mixer; mixer; (2) the
(2)
appropriate amount of water and admixture are added into the mixture for
the appropriate amount of water and admixture are added into the mixture for mixing; mixing; (3) cast
samples
(3) and allow
cast samples andthem
allowtothem
cure to
[71,76]. The dry-mix
cure [71,76]. dispersion
The dry-mix methodmethod
dispersion does notdoes
involve
not
dispersing fillers in an aqueous solution. Therefore, this method does not need
involve dispersing fillers in an aqueous solution. Therefore, this method does not need toto consider
the limitation
consider of the water–cement
the limitation ratio, which
of the water–cement ratio,iswhich
suitable for prepare
is suitable GRCCMs
for prepare with a
GRCCMs
high graphene concentration.
with a high graphene concentration.
2.3.2. Wet-Mix Dispersion
2.3.2. Wet-Mix Dispersion
Wet-mix dispersion is a technique for achieving good dispersion of graphene fillers by
Wet-mix dispersion is a technique for achieving good dispersion of graphene fillers
ultrasonication, electromagnetic/mechanical stirring, surfactant, or chemical surface modi-
by ultrasonication, electromagnetic/mechanical stirring, surfactant, or chemical surface
fication. Then the uniform solution is mixed with a cement matrix. The wet-mix dispersion
modification.
method can be Then the uniform
categorized intosolution
physicalisand mixed with adispersion.
chemical cement matrix. The wet-mix
The physical dis-
methods
persion method canmainly
in wet dispersion be categorized into physical and
involve ultrasonication andchemical dispersion. The physical
electromagnetic/mechanical stir-
methods in wet dispersion mainly involve ultrasonication and electromagnetic/mechani-
ring. The chemical methods involve chemical surface modification and surfactants, which
cal stirring.
usually The chemical
combine methods
with physical involvesuch
methods, chemical
as thesurface modification
combination and surfactants,
of surfactant/chemical
which usually combine with physical methods, such as the
surface modification and stirring, or surfactant/chemical surface modification combination of and
surfac-
stir-
tant/chemical surface modification and stirring, or surfactant/chemical
ring/ultrasonication. In the following, the physical and chemical methods involved in surface modifica-
tion and stirring/ultrasonication.
wet-dispersion are introduced and In discussed.
the following, the physical and chemical methods in-
volved in wet-dispersion are introduced and discussed.
(a) Ultrasonication
(a) Ultrasonication
Due to the high sound intensity, ultrasonication can stimulate a strong cavitation
Due
effect to aqueous
in an the high sound intensity,
solution ultrasonication
with a large can stimulate
number of cavitation a strong
bubbles. As cavitation
these bubblesef-
fect in an
burst, aqueous
a micro jet solution withwhich
is produced a largewill
number
crushofthe
cavitation bubbles.inAs
solid particles these
the bubbles
liquid. The
burst, a micro jet
solid particles andis produced
liquid canwhich
then be willfully
crush the solid
mixed. particles
However, in the
heat liquid. Theduring
is generated solid
the ultrasonic
particles process.
and liquid To avoid
can then themixed.
be fully influence of heat,heat
However, the is
process is usually
generated duringconducted
the ultra-
in theprocess.
sonic ice bathTo[77]. Prabavathy
avoid et al.of
the influence [78] added
heat, rGO powder
the process to 100
is usually mL of a 1:1
conducted water–
in the ice
ethanol mixture. Homogeneous dispersion is achieved by sonication of the mixture for
approximately 30 min. The rGO suspension was aged for 6 h to evaporate ethanol and
the suspension remained stable even after the aging period. Xu et al. [34] sonicated GNP
in deionized water for 2 h to obtain an aqueous dispersion. The solution was then mixed
with cement immediately after stirring for 10 min by using a high-speed homogenizer.
Liu et al. [79] mixed polycarboxylate superplasticizer (PC) with GNPs in an aqueous
solution and treated it with ultrasonication. It was found that GNPs were well dispersed in
an aqueous solution after ultrasonic treatment.
(b) Electromagnetic/Mechanical Stirring
Electromagnetic stirring is mainly used for stirring and heating low viscosity liquids
or solid–liquid mixtures. Akarsh et al. [80] made an aqueous solution of GO by electro-
magnetic stirrer at 600 to 1000 rpm. Because of the functional group, GOs were dispersed
without any surfactant. Rehman et al. [81] first treated the GNP solution with ultrason-
ication and then stirred it for 1 h using an electromagnetic stirrer to have homogenous
dispersion of the reinforcements. Then, the cement was added to the GNP suspension to
(b) Electromagnetic/Mechanical Stirring
Electromagnetic stirring is mainly used for stirring and heating low viscosity liquids
or solid–liquid mixtures. Akarsh et al. [80] made an aqueous solution of GO by electro-
magnetic stirrer at 600 to 1000 rpm. Because of the functional group, GOs were dispersed
Nanomaterials 2021, 11, 3220 without any surfactant. Rehman et al. [81] first treated the GNP solution with ultrasoni- 8 of 31
cation and then stirred it for 1 h using an electromagnetic stirrer to have homogenous
dispersion of the reinforcements. Then, the cement was added to the GNP suspension to
fabricate experimental samples. Li et al. [58,82] used a high-speed shear mixer to prepare
fabricatepaste
cement experimental
samples. samples. Li et al. [58,82]
After sonication of the used a high-speed
graphene solution,shear mixer
cement to prepare
powder was
cement paste samples. After sonication
added, and high-speed shear mixing was performed. of the graphene solution, cement powder was
added, and high-speed shear mixing was performed.
(c) Surfactants
(c) Surfactants
In
In addition
addition to to physical
physical methods,
methods,researchers
researchersalso alsoadd
addsurfactants,
surfactants,suchsuchasas methyl-
methylcel-
cellulose
lulose (MC) (MC) [26],
[26], sodium
sodium dodecyl
dodecyl benzene
benzene sulfonate
sulfonate (SDBS)(SDBS)
[44],[44], lignosulfonate
lignosulfonate (LS) (LS)
[83],
[83], naphthalene superplasticizer (NS) [84] and PC [83,85,86], to
naphthalene superplasticizer (NS) [84] and PC [83,85,86], to prepare CCMs with improved prepare CCMs with im-
proved dispersion. Surfactants can maintain the intact structure of
dispersion. Surfactants can maintain the intact structure of graphene filler with no dam- graphene filler with no
damage. Surfactants can be roughly divided into ionic and
age. Surfactants can be roughly divided into ionic and non-ionic. SDBS and PC are non-ionic. SDBS and PC are
ionic
ionic surfactants
surfactants that that can
can make
make graphene
graphene havehave good
good dispersion
dispersion in in an
an alkaline
alkaline solution.
solution.
Zhao
Zhao etet al.
al. [83]
[83]used
usedPC,PC,LS,LS,and
and polycondensate
polycondensate of b-naphthalene
of b-naphthalene sulfonate
sulfonate formalde-
formaldehyde
hyde
(PNS)(PNS) as surfactants
as surfactants to disperse
to disperse GO in solvent.
GO in solvent. The observation
The observation indicatedindicated that PC-
that PC-modified
modified
GO had improved dispersion in cement matrix compared with PNS and LS. Babak etLS.
GO had improved dispersion in cement matrix compared with PNS and Ba-
al. [87]
bak et al. [87] used PC to have a better dispersion of GO. The observation
used PC to have a better dispersion of GO. The observation of the fracture surface of the of the fracture
surface
sample of the sample
indicated that indicated
GOs werethat wellGOs were well
dispersed dispersed
without without agglomeration.
agglomeration. Zhai et al. [88]
Zhai
usedet sixal.dispersants
[88] used six in dispersants
combinationinwith combination
ultrasonic with ultrasonic
treatment treatmentdisperse
to uniformly to uniformlyrGO
disperse
into a cementrGO into
base.aTheir
cement base. Theirresults
experimental experimental
indicated results indicated
that NS was thethatbestNS was the
surfactant
best surfactantrGO.
for dispersing for dispersing
Figure 8 showsrGO. the
Figure 8 shows
UV-Vis the UV-Vis
spectroscopy spectroscopy
of two of two gra-
graphene suspensions
phene
with andsuspensions with and[69].
without surfactant without
Fromsurfactant [69]. From
the comparison, it isthe comparison,
obvious it is obvious
that graphene fillers
that graphene fillers had a better dispersion in the
had a better dispersion in the suspension containing surfactants. suspension containing surfactants.
Figure 8. UV-Vis spectroscopy of graphene suspensions with and without surfactants. Reprinted
with permission from Ref. [69]. Copyright 2018 Elsevier.
(d) Chemical Surface Modification

The presence of some functional groups such as hydroxyl (–OH), carboxyl (–COOH),
carbonyl groups(C=O), epoxy groups (–O–), etc., on graphene and its derivatives can react with
each other or some other molecules. These reactions can be used to functionalize the surface of
graphene fillers with covalent bonds. Ma et al. [89] functionalized GO with NH2 and added
the filler into cement mortar. Mercury intrusion porosimetry (MIP) found that GO and the
functionalizing groups filled the pore in the CCMs. The functionalization by NH2 enhanced the
interaction between GO and the cement matrix. Li et al. [90] prepared GO with polycarboxylic
acid superplasticizer for surface functionalization. The findings of the experiment showed
that the functionalized GOs were well dispersed in the CCMs. The adsorption behavior of
chemically functionalized GO with three different polyether amine branched-chain lengths
was studied in comparison with GO on cement by Wang et al. [91,92]. Figure 9 shows the
chemically functionalized GO obtained by the condensation reaction of GO with polyether
amines. The results of the experiment indicated that the chemically functionalized GO improved
the dispersion.
GO with polycarboxylic acid superplasticizer for surface functionalization. The findings
of the experiment showed that the functionalized GOs were well dispersed in the CCMs.
The adsorption behavior of chemically functionalized GO with three different polyether
amine branched-chain lengths was studied in comparison with GO on cement by Wang
et al. [91,92]. Figure 9 shows the chemically functionalized GO obtained by the condensa-
9 of 31
tion reaction of GO with polyether amines. The results of the experiment indicated that
the chemically functionalized GO improved the dispersion.
Figure 9. Schematic illustration of chemically functionalized GO. Reprinted from Ref. [91].
Figure 9. Schematic illustration of chemically functionalized GO. Reprinted from Ref. [91].
Although chemical surface modification of graphene fillers can significantly improve
Although chemical surface modification of graphene fillers can significantly improve
their solubility and wettability and reduce agglomeration, the original excellent properties
their solubility and wettability and reduce agglomeration, the original excellent properties
of the graphene fillers can be easily altered in the modification process.
of the graphene fillers can be easily altered in the modification process.
2.4. Characterization
2.4. Characterization
After fabrication of GRCCMs, it is evidenced that the dispersion of graphene fillers,
After fabrication
the hydration process,ofand
GRCCMs, it is evidenced
the crystallization that which
reaction the dispersion
occurredofbetween
graphene thefillers,
fillers
the hydration process, and the crystallization reaction which occurred
and the cement matrix, etc., could significantly affect both the mechanical and physicalbetween the fillers
and the cement
properties of thematrix,
GRCCMs. etc., For
could significantly
example, the pore affect both the
structures mechanical
in the CCMs, i.e., andsize,
physical
distri-
properties
bution, and ofconnection,
the GRCCMs. are For example,
highly relatedthe porehydration
to the structures in the and
process CCMs, i.e., size,
a reaction distri-
occurred
bution,
between and
theconnection, are and
graphene filler highly therelated
cementto the hydration
matrix. process
Accordingly, and a reaction
the investigation of oc-
the
curred between
dispersion, the graphene
hydration, filler and
and reaction the composites
in the cement matrix.can Accordingly, the investigation
provide insightful information
of
onthe
thedispersion,
mechanismhydration,
that underpinand reaction in the composites
the reinforcing can
effects of the provide fillers.
graphene insightful infor-
Therefore,
mation
the work onontheusing
mechanism that underpin the reinforcing
some methods/techniques, including effects
thermalofanalysis,
the graphene fillers.
X-ray diffrac-
Therefore,
tion (XRD)the work on
analysis, using
X-ray some methods/techniques,
Photoelectron Spectroscopy (XPS), including thermal analysis,
Fourier-transform X-
infrared
ray diffraction
(FTIR) (XRD)analysis,
spectroscopy analysis,RamanX-ray spectroscopy,
PhotoelectronNuclear
Spectroscopy
Magnetic(XPS), Fourier-trans-
Resonance (NMR)
form infrared (FTIR)
spectroscopy, Mercury spectroscopy analysis, Raman
Intrusion Porosimetry (MIP),spectroscopy, Nuclear
Scanning Electron Magnetic(SEM)
Microscopy Res-
and Friction
onance (NMR)Force Microscopy
spectroscopy, (FFM),Intrusion
Mercury to characterize and investigate
Porosimetry the GRCCMs
(MIP), Scanning Electronis
introduced and
Microscopy (SEM) discussed.
and Friction Force Microscopy (FFM), to characterize and investigate
the GRCCMs is introduced and discussed.
2.4.1. Thermal Analysis
2.4.1. There
ThermalareAnalysis
mainly four methods involved for thermal analysis of GRCCMs, includ-
ing thermogravimetric
There are mainly fouranalysis
methods(TGA), derivative
involved thermogravimetric
for thermal (DTG), differential
analysis of GRCCMs, including
thermal analysis (DTA), and differential scanning calorimetry (DSC). Thermal
thermogravimetric analysis (TGA), derivative thermogravimetric (DTG), differential analysis is a
ther-
method to estimate the variation of material properties with temperature and
mal analysis (DTA), and differential scanning calorimetry (DSC). Thermal analysis is a heat flux,
and the hydration process of GRCCMs can be examined by the thermal analysis.
TGA plots the change of mass in terms of temperature while the sample is subjected to a
controlled temperature. It can provide information on phase transition, absorption (desorption),
thermal decomposition, etc. In contrast, DTG measures the mass loss rate (i.e., −dm/dt) in
terms of the temperature. Compared to TGA, the DTG curve can be used to identify the critical
temperature for peaks of mass loss rate. Wang et al. [26] conducted TG/DTG analysis for plain
cement and GNP-reinforced CCMs at 7 and 28 days. It is found that the amounts of Ca(OH)2
and amorphous phases in GNP-reinforced CCMs were increased at the age of 7 days, indicating
the acceleration of the hydration process. Figure 10 shows the TGA and DTG analysis for
Ca(OH)2 decomposition in GO/rGO reinforced by CCMs by Qureshi and Panesar [93]. From
the figure, it can be seen that the mass loss of GO reinforced CCMs with respect to Ca(OH)2
was greater than that of rGO reinforced CCMs. This indicates that rGO may have a better
reinforcing effect compared to GO.
TG/DTG analysis for plain cement and GNP-reinforced CCMs at 7 and 28 days. It is found
that the amounts of Ca(OH)2 and amorphous phases in GNP-reinforced CCMs were in-
creased at the age of 7 days, indicating the acceleration of the hydration process. Figure
10 shows the TGA and DTG analysis for Ca(OH) 2 decomposition in GO/rGO reinforced
by CCMs by Qureshi and Panesar [93]. From the figure, it can be seen that the mass loss
10 of 31
of GO reinforced CCMs with respect to Ca(OH) 2 was greater than that of rGO reinforced
CCMs. This indicates that rGO may have a better reinforcing effect compared to GO.
Figure 10.
10. TGA
TGAand
andDTGDTG curves forfor
curves GOGOor rGO reinforced
or rGO CCMs
reinforced at 28atdays.
CCMs Reprinted
28 days. with with
Reprinted
permission from Ref. [93]. Copyright 2019 Elsevier.
Unlike TGA and and DTG

DTG measuring
measuring temperatures
temperaturesdirectly,
directly, DTA
DTA measured
measured thethe temper-
temper-
ature difference
difference between
betweenaasample
sampleand
anda thermally
a thermally inert reference material when bothboth
inert reference material when the
the above
above two two materials
materials are undergoing
are undergoing a programmed
a programmed temperature.
temperature. This This analysis
analysis can
can pro-
provide
vide information
information on on transformations
transformations likecrystallization,
like crystallization,glass
glasstransitions,
transitions, sublimation,
sublimation,
melting, etc. Sardar et al. [94] determined the the properties
properties of
of GO/cement
GO/cement composites at high
temperatures using the TGA/ TGA/DTADTA method. From the DTA DTA curves, as shown in Figure 11,
it can be identified that water loss from carboaluminate
carboaluminate hydrate and C-S-H occurred at
180–300 ◦°C,
C, dehydroxylation of portlandite (calcium hydroxide) at 430–480 °C, ◦ C, and decar-
and decar-
bonation of of calcium
calcium carbonate
carbonate atat 600–780
600–780 °C.◦ C. Using the TG-DTA curve, Wang et al. [95]
bonation Using the TG-DTA curve, Wang et al. [95]
identified that
identified that the
the dispersion
dispersion ofof GO
GO had
had aa limited
limited influence
influence on
on the
the number
number of of hydration
hydration
products of
products of the
the cement
cement composite
composite atat 33 days,
days, while
while at
at 90
90 days,
days, the
the addition
addition of
of 0.01
0.01 wt%
wt% GOGO
promoted the hydration.
promoted the hydration.
Figure
Figure 11. TGA/DTA
TGA/DTAcurves
curvesof
ofplain
plain cement
cement and
and GO/cement
GO/cementcomposites.
composites. Reprinted
Reprinted from
from Ref.
Ref. [94].
[94].
Instead of
Instead of measuring
measuring the the temperature
temperature difference,
difference, DSC
DSC measures
measures the difference in
heat (energy) needed to keep both the reference material
heat (energy) needed to keep both the reference material and the sample and the sample
at theatsame
the same
tem-
temperature. It is an indication of the occurrence of glass transition, crystallization,
perature. It is an indication of the occurrence of glass transition, crystallization, oxidation, ox-
idation,
and and chemical
chemical reactions.reactions.
Wang et al. Wang
[96] et al. [96]
used DSCused DSCthe
to study to mechanisms
study the mechanisms of
of the effects
theGO
of effects of GOfrom
on CCMs on CCMs from theperspective.
the hydration hydration perspective.
As shown in As shown
Figure 12, in
theFigure 12, the
endothermic
endothermic ◦ C denoted the decomposition of Ca(OH) . As the GO contents in
peak at 457 °Cpeak at 457the
denoted decomposition of Ca(OH)2. As the GO contents 2 in the modified
cement increased, the characteristic peak generated by the decomposition of Ca(OH) 2
dropped. Such an observation suggests that the addition of GO decreased the temperature
for the decomposition of Ca(OH)2 and affects the hydration process. However, Wang et
al. [97] conducted TG-DSC analysis on GO/cement composites at 28 days to study the
Figure 11. TGA/DTA curves of plain cement and GO/cement composites. Reprinted from Ref. [94].
Instead of measuring the temperature difference, DSC measures the difference in

heat (energy) needed to keep both the reference material and the sample at the same tem-
perature. It is an indication of the occurrence of glass transition, crystallization, oxidation,
and chemical reactions. Wang et al. [96] used DSC to study the mechanisms of the effects
of GO on CCMs from the hydration perspective. As shown in Figure 12, the endothermic
peak at 457 °C denoted the decomposition of Ca(OH)2. As the GO contents in the modified
the modified
cement cementthe
increased, increased, the characteristic
characteristic peak generated
peak generated by the decomposition
by the decomposition of Ca(OH) of2
Ca(OH)
dropped. 2 dropped. Such an observation
Such an observation suggests that suggests that the
the addition of addition of GOthe
GO decreased decreased
temperaturethe
temperature for the decomposition
for the decomposition of Ca(OH)2ofand Ca(OH) 2 and
affects the affects the hydration
hydration process. However,
process. However, Wang et
Wang et al. [97] conducted TG-DSC analysis on GO/cement composites
al. [97] conducted TG-DSC analysis on GO/cement composites at 28 days to study at 28 days to study
the
the hydration reaction and found that GO had limited effects on the hydration
hydration reaction and found that GO had limited effects on the hydration process. The process.
The
aboveabove different
different observations
observations maymay be attributed
be attributed to preparation
to the the preparation of the
of the composites
composites and
and the dispersion
the dispersion of graphene
of the the graphene fillers
fillers in matrix.
in the the matrix.
Figure12.
Figure 12. DSC
DSCcurve
curveofofGO/cement
GO/cementcomposites
compositesatat2828days.
days.Reprinted
Reprintedwith
with permission
permission from
from Ref.
Ref. [96].
[96]. Copyright
Copyright 2016 Elsevier.
2016 Elsevier.
2.4.2.
2.4.2. X-ray
X-ray Diffraction
Diffraction (XRD)
(XRD) Analysis
Analysis
To
To further investigate the hydration
further investigate the hydration process,
process, X-ray
X-ray Diffraction
Diffraction analysis,
analysis, which
which isis aa
non-destructive method, can be used to determine the crystalline structure
non-destructive method, can be used to determine the crystalline structure of GRCCMs.of GRCCMs.
XRD
XRDcan cancharacterize
characterizethe
thedegree
degree ofof
hydration of of
hydration GRCCMs
GRCCMs by by
monitoring the change
monitoring of the
the change of
peak intensity
the peak for crystalline
intensity structure
for crystalline of hydration
structure products.
of hydration products.
Horszczaruk et al. [22] used XRD to investigate the phase transition and crystalline
hydration products of plain and GO-reinforced CCMs, respectively. Figure 13 demonstrates
the XRD patterns for the two composite samples with different hydration times. As
the hydration process continues, the intensity of the peaks attributed to un-hydrated
silicates (C3 S) and belite (C2 S) is decreased. New peaks with respect to the formation of
portlandite (Ca(OH)2 ) and ettringite (C6 AS3 H32 ) appeared. Since no significant difference
was observed between the GO/cement and plain cement samples, the XRD results indicated
that the crystal phase did not change after the addition of GO fillers.
Qureshi and Panesar [93] examined GO and rGO-reinforced CCMs at different curing
times by XRD. The typical hydration products, including C6 AS3 H32 , Ca(OH)2 , CH, C3 S,
and C2 S, were detected at all ages. The intensity of CH phases enhanced with the increases
in the GO and rGO concentration and curing time. The intensities of the C6 AS3 H32 phases
diminished with the hydration process and demonstrated an enhanced intensity in the
rGO-reinforced CCMs. Yaseen et al. [98] employed XRD to identify the crystalline phases
of the solid products. It is observed that the intensities of the CH and CaCO3 peaks with
GO and/or rGO reinforcements were higher than the peaks without any reinforcements.
The CaCO3 peak intensity increased with the GO and/or rGO addition. The above XRD
observations suggest that the addition of GO and/or rGO can enhance the curing and
hydration process in the cement composites.
hydration products of plain and GO-reinforced CCMs, respectively. Figure 13 demon-
strates the XRD patterns for the two composite samples with different hydration times.
As the hydration process continues, the intensity of the peaks attributed to un-hydrated
silicates (C3S) and belite (C2S) is decreased. New peaks with respect to the formation of
Nanomaterials 2021, 11, 3220 portlandite (Ca(OH)2) and ettringite (C6AS3H32) appeared. Since no significant difference
12 of 31
was observed between the GO/cement and plain cement samples, the XRD results indi-
cated that the crystal phase did not change after the addition of GO fillers.
plain cement
Figure 13. XRD result of plain cement (reference)
(reference)and
andGO-reinforced
GO-reinforcedCCMs.
CCMs.Reprinted
Reprintedwith
withpermis-
per-
mission
sion fromfrom
Ref.Ref.
[22].[22]. Copyright
Elsevier.
2.4.3.Qureshi
X-ray Photoelectron
and Panesar Spectroscopy
[93] examined(XPS)GO and rGO-reinforced CCMs at different cur-
ing times
XPS isbya XRD. The typical
spectroscopic hydration
technique products,
for the includingofCsurfaces,
characterization 6AS3H32, which
Ca(OH) , CH, C3to
is2helpful S,
and C2S,the
identify were detected
elements at allor
within ages. Thesurface
on the intensity
of of CH phases
a material, enhanced
as well with
as their the increases
chemical bonds.
in thecan
XPS GObeandusedrGO to concentration and curing
study the adsorption time. The
properties andintensities
chemicalof the C 6AS
reactions of3H 32 phases
graphene
fillers on cement
diminished with andthe can help further
hydration processdetermine the connection
and demonstrated between graphene
an enhanced intensity fillers
in the
and cement. This
rGO-reinforced can provide
CCMs. Yaseeninformation on the interaction
et al. [98] employed between
XRD to identify thethe graphene
crystalline filler
phases
and
of thethesolid
cement matrix.It is observed that the intensities of the CH and CaCO 3 peaks with
products.
Wang et
GO and/or rGOal. [51,96] used XPSwere
reinforcements to study thethan
higher adsorption characteristics
the peaks without anyand mechanisms
reinforcements.
of GO-modified cement composites. Figure 14 demonstrates the
The CaCO3 peak intensity increased with the GO and/or rGO addition. The aboveXPS results of the cement
XRD
surface of cement
observations suggestwith and
that thewithout
additionGO. From
of GO the rGO
and/or figure,
canitenhance
can be seen that the
the curing and Sihy-
2p
core-levels
dration processpresented
in the not onlycomposites.
cement an intensity reduction, but also a chemical shift towards
lower binding energy, indicating a reduction in the former Si-oxide (peak around 103 eV).
The intensities of both Si 2p and Ca 2p decreased after the adsorption of GO nanosheets,
indicating the adsorption of GO on cement. With the increase of the GO concentration,
the production of Ca(HCOO)2 increased. Li et al. [82] also investigated the adsorption of
GO fillers onto the surface of cement by XPS, in which Ca and Si were used as marker
elements. Their experimental studies showed that with the addition of 0.04 wt% GO, the
intensities for the two elements were unchanged, indicating very limited adsorption of
GO on cement surface. Yaseen et al. [98] prepared GO and rGO-reinforced CCMs and
examined the interaction during the carbonation reaction at 7 and 28 days by XPS. Because
of the functional groups, the dispersion of GO resulted in a faster carbonation and a greater
CaCO3 generation.
fillers onto the surface of cement by XPS, in which Ca and Si were used as marker ele-
ments. Their experimental studies showed that with the addition of 0.04 wt% GO, the
intensities for the two elements were unchanged, indicating very limited adsorption of
GO on cement surface. Yaseen et al. [98] prepared GO and rGO-reinforced CCMs and
Nanomaterials 2021, 11, 3220 examined the interaction during the carbonation reaction at 7 and 28 days by XPS. Because
13 of 31
of the functional groups, the dispersion of GO resulted in a faster carbonation and a
greater CaCO3 generation.
Figure 14. XPS

Figure 14. XPS results
results of
ofcement
cementsurface
surfacewith
withand
andwithout
without GO
GO (a)(a) Si 2p;
Si 2p; (b)(b)
Ca Ca
2p.2p. Reprinted
Reprinted withwith permission
permission fromfrom
Ref. Ref.
[51].
[51]. Copyright 2016 RSC Publishing.
Copyright 2016 RSC Publishing.
2.4.4.
2.4.4. Fourier-Transform
Fourier-Transform Infrared (FTIR) Spectroscopy
FTIR spectroscopy isisan
FTIR spectroscopy anexamination
examinationmethodmethodtoto gain
gain thethe infrared
infrared spectrum
spectrum of ab-
of absorp-
sorption or emission
tion or emission of a of a material.
material. TheThe spectra
spectra profile
profile of the
of the examined
examined sample
sample cancan
be be used
used to
to compare
compare withwith
the the
onesones indatabase
in the the database to screen
to screen components
components in the sample.
in the sample. Unlike
Unlike thermal
thermal analysis
analysis and XRD,andFTIRXRD, FTIR can quantitatively
can quantitatively identify theof occurrence
identify the occurrence of bond
bond stretching and
interactions
stretching instead
and of their instead
interactions extent. Ho et al.extent.
of their [42] conducted
Ho et al.an FTIR
[42] investigation
conducted on CCMs
an FTIR inves-
with different
tigation on CCMs contents of graphene.
with different As demonstrated
contents of graphene. As in Figure 15, the intensities
demonstrated of the
in Figure 15,
spectra denoting CSH gels, CH, and
intensities of the spectra denoting CSH gels, CaCO in GRCCMs were stronger than
3 CH, and CaCO3 in GRCCMs were stronger those of plain
Nanomaterials 2021, 11, 3220 samples, 14 of 32
than thoseindicating an improved
of plain samples, enhancement
indicating in mechanical
an improved properties.
enhancement This was ascribed
in mechanical proper-
to the
ties. facilitated
This hydration
was ascribed to theinfacilitated
the reinforced composites.
hydration in the reinforced composites.
Figure 15.
Figure 15. FTIR
FTIR spectra
spectra of
of cement
cement composites
composites with
with different
different graphene
graphene concentrations
concentrations (0%,
(0%, 0.03%,
0.03%,
0.07% and
0.07% and 0.3%)
0.3%) at
at 28
28 days.
days. Reprinted
Reprinted with
with permission
permission from
from Ref.
Ref. [42].
[42]. Copyright
Copyright 2020
2020 Elsevier.
Elsevier.
al. [51,96]
Wang et al. [51,96] conducted
conducted FTIRFTIR analysis
analysis for
for GO
GO and
and GO-modified
GO-modified CCMs
CCMs with
with
different concentrations. According to the FTIR analysis, with the the increase
increase in GO concen-
peak at
tration, the peak at ~3650 cm−–11 corresponding
~3650 cm corresponding to
to –OH
–OH in Ca(OH)22 became
became more
more obvious.
Compared to GO-reinforced CCMs, the –COOH in GO underwent a chemical reaction to
generate a new component including –COO– in the GO reinforced CCMs. Yang et al. [99]
compared the FTIR spectrum for GO and different cement samples. After adding GO, only
a small amount of CO3 was generated, with no other changes occurring.
Compared to GO-reinforced CCMs, the –COOH in GO underwent a chemical reaction to

generate a new component including –COO− in the GO reinforced CCMs. Yang et al. [99]
compared the FTIR spectrum for GO and different cement samples. After adding GO, only
a small amount of CO3 was generated, with no other changes occurring.
2.4.5. Raman Spectroscopy

Raman spectroscopy is another non-destructive analytical method that provides in-
formation on phase and polymorphy, molecular interactions, chemical structure, and
crystallinity. It is a useful technique to characterize the structural configuration of GRC-
CMs. Hou et al. [45] used Raman spectroscopy to study the influences of the hydration
reaction of cement matrix after adding graphene and GO (as shown in Figure 16). It is
observed that the plain cement sample showed a distinctive Ca(OH)2 characteristic peak
because of the hydration of C3 S at the early stage, whereas, after the addition of GO, the
peak almost vanished because of the chemical reaction of Ca2+ with COOH in GO to form
Ca(HCOO)2 .
Horszczaruk et al. [22] Raman spectra of GO/cement composites demonstrated two
peaks (D, G). An additional band appeared between D and G, which was attributed to
the formation of alite. The results showed that GO interacted well with the hydration
products of Portland cement. Phrompet et al. [31] performed Raman spectra analysis for
rGO/cement composites. The intensity of the D and G band peaks increased significantly
with the increasing rGO contents, which confirmed that rGO combined effectively with the
C3AH6 cement to form a nanocomposite.
Figure 16.
Figure 16. Raman
Ramanresults
resultsofof(1)
(1)Plain
Plaincement
cementsample;
sample;(2)(2)
GO;GO;
(3)(3) Graphene/cement
Graphene/cement sample.
sample. Reprinted
Reprinted
with with permission
permission fromCopyright
from Ref. [45]. Ref. [45]. 2017
Elsevier.
2.4.6.
2.4.6. Nuclear Magnetic Resonance (NMR) Spectroscopy
Spectroscopy
NMR
NMR spectroscopy, which is an analytical chemistry
spectroscopy, which is an analytical chemistrymethod
methodto to obtain
obtain the
the purity
purity andand
content, has been widely used to analyse the C-S-H structure in
analyse the C-S-H structure in CCMs. CCMs. Yang et
et al.
al. [99]
[99]
employed
employed NMRNMRto tostudy
studythe theC-S-H
C-S-Hstructure
structure inin
GO-reinforced
GO-reinforcedCCMsCCMs at 14
at and 28 days
14 and 28 days(as
shown in Figure
(as shown in Figure Q0 , Q
17). 17). 1
Q0, and Q2 represented
Q1 and Q2 represented dehydrated cement,
dehydrated the end-chain
cement, the end-chainsilicate
sil-
tetrahedral, and middle-chain
icate tetrahedral, silicate,
and middle-chain respectively.
silicate, The results
respectively. showed
The results that thethat
showed hydration
the hy-
degree
drationof GO-modified
degree cementcement
of GO-modified samples was higher
samples than that
was higher thanof plain
that cement
of plain samples.
cement sam-
Wang and Deng [55] prepared GNP/cement composites and monitored
ples. Wang and Deng [55] prepared GNP/cement composites and monitored the hydra- the hydration
process by NMR.
tion process Their Their
by NMR. resultsresults
also suggested that GNP
also suggested thatenhanced the hydration
GNP enhanced reactionre-
the hydration of
the cement and produced more hydration products.
action of the cement and produced more hydration products.
employed NMR to study the C-S-H structure in GO-reinforced CCMs at 14 and 28 days
(as shown in Figure 17). Q0, Q1 and Q2 represented dehydrated cement, the end-chain sil-
icate tetrahedral, and middle-chain silicate, respectively. The results showed that the hy-
dration degree of GO-modified cement samples was higher than that of plain cement sam-
Nanomaterials 2021, 11, 3220 ples. Wang and Deng [55] prepared GNP/cement composites and monitored the 15 hydra-
of 31
tion process by NMR. Their results also suggested that GNP enhanced the hydration re-
action of the cement and produced more hydration products.
17.2929Si-NMR
Figure17.
Figure Si-NMRspectra
spectraofofGO/cement
GO/cementcomposite
compositespecimens
specimensatat14
14and
and28
28days.
days.Reprinted
Reprintedwith
with
permissionfrom
permission fromRef.
Ref.[99].
[99].Copyright
Copyright2017
2017Elsevier.
Elsevier.
Xu
Xuetetal.al.
[100] performed
[100] performedNMR
NMR analysis of GO/cement
analysis of GO/cementcomposites and found
composites that GO
and found that
attracted Ca ions to generate jennite-like hydrates closed to GO sheets and promoted
GO attracted Ca ions to generate jennite-like hydrates closed to GO sheets and promoted the
formation of tobermorite-like hydrates far beyond GO sheets. Kang et al. [101] examined
the hydration of GO/cement composites by conducting an NMR analysis. Table 1 tabulates
the information obtained from the NMR results. The incorporation of 0.01 wt% and
0.05 wt% GO enhanced the hydration process of C3 S by 68.2% and 72.4%, respectively,
demonstrating GO’s beneficial effect on the hydration process.
Table 1. Results obtained from 29 Si MAS NMR spectroscopy. Reprinted with permission from Ref. [101]. Copyright
2019 Elsevier.
GO Content (wt%) Q0 (%) Q1 (%) Q2 (%) Q2 /Q1 MCL α (%)

0.00 45.20 27.02 27.78 1.03 4.056 54.8
0.01 32.12 36.46 32.42 0.89 3.778 68.2
0.05 27.65 39.98 32.37 0.81 3.619 72.4
2.4.7. Mercury Intrusion Porosimetry (MIP)

MIP is a destructive method adopted to obtain the volume of pores, surface area of
a material, total connected porosity, and pore size distribution. It has been commonly
employed to study the microstructure of GRCCMs. The electrical and dielectric properties
of GRCCMs are closely related to the size, distribution, and connectivity of pores in the
composites. Because the pore structure determines the charge transport properties of
GRCCMs, the testing and characterization of the pore structure are essential to provide
information to improve the material properties of multifunctional GRCCMs.
The effect of the incorporation of rGO on the pore refinement of Portland cement was
studied by Murugan et al. [102] via MIP. Table 2 tabulates the information obtained from
the MIP results. The OPC paste with well-dispersed rGO was found to reduce the capillary
pores by 32.1%. However, the rGO addition increased the gel pores by up to 36.5%.
Table 2. Pore structure feature of rGO-reinforced cement paste. Reprinted with permission from Ref. [102]. Copyright
2016 Elsevier.
Gel Pores <10 nm in Capillary Pores (10 Threshold Diameter Most Likely Diameter
Paste
mm3 /g nm–10 µm) in mm3 /g in nm in nm
Control 10.69 48.58 26.8 14.7
rGO 14.60 33.01 20.7 12.9
n-Al2 O3 26.97 60.58 39.1 27.1
n-SiO2 23.42 57.76 28.6 20.4
Wang et al. [26,55,56,84] investigated the porosity and microstructure of GNP/cement

composites by the MIP technique. Figure 18 shows the pore size distribution for different
cement composite samples, in which V and G2 denoted pure cement samples and the
sample with GNP reinforcement. The addition of GNP remarkably improved the pore
structure of the CCMs. The average diameter and porosity of the reinforced CCMs de-
creased by up to 10% and 40%, respectively, after 28 days of curing when compared to the
plain cement sample.
The MIP results by Du et al. [103–105] reveal that the critical size in CCMs can be
reduced by more than 30% due to the addition of 2.5 wt% GNP. The nanoparticle size
of GNP reinforcement can facilitate the nucleation for cement hydration products. Tao
et al.’s [106] MIP investigation found that due to micro filling and nucleation provided by
the addition of GNP, the porosity of the reinforced CCMs decreased. However, when the
GNP concentration further increased, the porosity was increased because of agglomerations.
Nanomaterials 2021, 11, 3220 Liu et al.’s [44] MIP results revealed that the incorporation of graphene enhanced 17 ofthe
32
compactness and refined the microstructure of the CCMs.
Figure 18.
Figure 18. Pore
Poresize
sizedistribution
distributionofofGNP/cement
GNP/cementcomposites. Reprinted
composites. withwith
Reprinted permission fromfrom
permission Ref.
[55]. Copyright 2019 Elsevier.
Ref. [55]. Copyright 2019 Elsevier.
2.4.8. Scanning Electron Microscopy

Microscopy (SEM)(SEM)
The dispersion
dispersion of of graphene
graphene filler
filler in
in CCMs
CCMs plays
plays aa crucial
crucial role
role in
in their
their mechanical
mechanical and and
physical
physical conductivity.
conductivity.SEM SEMisisanan
electron
electron microscope
microscope thatthat
uses a focused
uses beam
a focused of electrons
beam of elec-
to scantothe
trons surface
scan of a sample.
the surface The dispersion
of a sample. of graphene
The dispersion filler in filler
of graphene CCMsincanCCMsbe studied
can be
by SEM, and the morphological characteristics, structure, and defects of
studied by SEM, and the morphological characteristics, structure, and defects of graphenegraphene filler can
be observed.
filler can be observed.
Jing
Jing et
et al.
al. [107]
[107] investigated
investigated the
the microstructures
microstructures of of plain
plain cement
cement andand GO-reinforced
GO-reinforced
cement
cement samples
samples by by SEM
SEM (as(as shown
shown in in Figure
Figure 19).
19). The
The image
image ofof the
the plain
plain cement
cement sample
sample
demonstrated that many micro-cracks and pores existed among the
demonstrated that many micro-cracks and pores existed among the crystals. In contrast, crystals. In contrast,
with the addition of GO, there existed lots of calcium silicate hydrate gel and rod-shaped
C6AS3H32 with no separated crystals being observed. The results showed that the samples
with GO had a compact microstructure and fewer pores and cracks. Such a comparison of
the SEM images suggested that the incorporation of the GO enhanced hydration and re-
The dispersion of graphene filler in CCMs plays a crucial role in their mechanical and
physical conductivity. SEM is an electron microscope that uses a focused beam of elec-
trons to scan the surface of a sample. The dispersion of graphene filler in CCMs can be
studied by SEM, and the morphological characteristics, structure, and defects of graphene
filler can be observed.
Jing et al. [107] investigated the microstructures of plain cement and GO-reinforced
cement samples by SEM (as shown in Figure 19). The image of the plain cement sample
demonstrated that many micro-cracks and pores existed among the crystals. In contrast,
with the
with the addition
addition of of GO,
GO, there
there existed
existed lots
lots of
of calcium
calcium silicate
silicate hydrate
hydrate gel
gel and
and rod-shaped
rod-shaped
C66AS33HH3232with
withnonoseparated
separated crystals
crystals being
being observed.
observed. The The results showed that the samples
samples
with GO had a compact
with compactmicrostructure
microstructureand andfewer
fewerpores
poresand andcracks.
cracks.Such
Such a comparison
a comparison of
thethe
of SEMSEM images
images suggested
suggestedthat thethe
that incorporation
incorporation of the GOGO
of the enhanced
enhancedhydration
hydrationandand re-
markably improved
remarkably improvedthe themicrostructure
microstructureof ofthe
thecement
cement sample.
sample. Alkhateb
Alkhateb et al. [108]
[108] used
used
SEM to have
have thethe surface
surface topography
topography and the composition
composition of GRCCMs.
GRCCMs. Tong et al. al. [109]
[109]
fillers to
used GNP as fillers to reinforce
reinforce CCMs.
CCMs. A nano-scale
nano-scale characterization,
characterization, which
which was
was focused
focused
on the
on the microstructure
microstructureofofthe thecement
cementpaste
paste around
around thethe graphene
graphene reinforcements,
reinforcements, waswas car-
carried
out
riedtoout
analyze the reinforcing
to analyze mechanism.
the reinforcing Pei et Pei
mechanism. al. [110]
et al. modified CCMsCCMs
[110] modified by introducing
by intro-
high-quality graphene
ducing high-quality and PVA.
graphene andBy the By
PVA. analysis of the of
the analysis SEMthe images, it wasitfound
SEM images, was foundthat
graphene
that graphene and cement
and cement werewere
tightly bound
tightly in theincomposites.
bound the composites.

Figure 19. SEM images of cement paste
paste after
after 28
28 days:
days: (a) 0 wt% GO; (b) 0.6 wt%
wt% GO.
GO. Reprinted
Reprinted with
with
2.4.9. Friction
2.4.9. Friction Force
Force Microscopy
Microscopy (FFM)
(FFM)
Apart from
Apart from SEM,
SEM, FFM
FFM is
is another
another powerful
powerful tooltool for
for the
the investigation
investigation of of the
the topology
topology
and morphology
and morphology of GRCCMs.
GRCCMs. FFM is a type of of scanning
scanning probe
probe microscopy
microscopy with with aa very
very
high-resolution. It has been adopted as a technique
high-resolution. technique to to study
study thethe physical
physical and
and chemical
chemical
propertiesof
properties ofGRCCMs.
GRCCMs.Horszczaruk
Horszczaruketet al.al. [22]
[22] used
used FFM FFM to examine
to examine the early
the early age me-
age mechan-
chanical
ical response
response of theofcement
the cement
mortarmortar modified
modified withwith
GO. GO.
FromFromtheirtheir topology
topology images,
images, the
the distributions
distributions of Young’s
of Young’s modulus
modulus fortwo
for the thecomposite
two compositesamplessamples were estimated.
were estimated. FigureFig-
20
ure 20 the
shows showsFFM the FFMof
image image
GNPof GNP reinforced
reinforced CCMs by CCMs by Alkhateb
Alkhateb et al.
et al. [108] The[108]
FFMThe FFM
images
disclosed the C-S-H
images disclosed thestructures with both
C-S-H structures high-density
with and low-density.
both high-density The phase
and low-density. Theimage
phase
provided information
image provided on the stiffness
information variation
on the stiffness of the specimen.
variation The dark
of the specimen. The brown
dark colour
brown
reflected the deepthe
colour reflected topography, while thewhile
deep topography, brightthepink colour
bright pinkreflected the high topography.
colour reflected the high to-
Particularly, the image identified
pography. Particularly, the imagethe GNP filler
identified the at the filler
GNP top-right
at thecorner. It was
top-right confirmed
corner. It was
that the GNP correlated with the high-stiffness phase topology.
confirmed that the GNP correlated with the high-stiffness phase topology.
Figure 20.
Figure 20. FFM
FFM images
imagesofofGNP/cement
GNP/cement composites:
composites: (a)
(a) Height
Height image;
image; (b)
(b) Phase
Phaseimage.
image. Reprinted
Reprinted
with permission
with permission from
from Ref.
Ref. [108].
[108]. Copyright
Copyright 2013
2013 American
AmericanSociety
Society of
ofCivil
CivilEngineers.
Engineers.
3. Electrical Property
It is evidenced that the addition of graphene fillers into the cement matrix signifi-
cantly increases/decreases the electrical conductivity/resistivity of the reinforced compo-
sites. Such an increase in the electrical conductivity can significantly promote the applica-
tion and sensitivity of such CCMs in detection of water/chloride ion penetration and cor-
3. Electrical Property
It is evidenced that the addition of graphene fillers into the cement matrix significantly
increases/decreases the electrical conductivity/resistivity of the reinforced composites.
Such an increase in the electrical conductivity can significantly promote the application
and sensitivity of such CCMs in detection of water/chloride ion penetration and corrosion
occurred in the concrete structures. Table 3 summarizes the work on investigating the
electrical properties of GRCCMs.
Table 3. Summary of studies on electrical properties of GRCCMs.
Filler Type Matrix Preparation Electrical Properties Ref.

The addition of 1 vol% of graphene enhanced the electrical
Graphene Paste Dry-mix conductivity by 3 orders. With 10 vol% graphene, the [30]
conductivity was 10−2 S/m.
The electrical conductivity of the composites demonstrated
Graphene Paste Wet-mix [43]
S-shaped curves.
The percolation threshold for electrical resistivity of the
composites was close to 2 vol%.
The electrical conductivity of rGO/cement paste was
rGO Paste/Mortar Wet-mix [53]
increased by 23%.
The cement paste with 0.08 wt% GO demonstrated much
GO Paste Wet-mix [58]
lower electrical resistivity.
The electrical resistivity of GNP/cement composites with 2.0
GNPs Mortar Dry-mix [72]
vol% GNP was lowered to 100.8 Ω·cm.
When the rGO content was 2.00 wt%, the electrical resistivity
rGO Mortar Wet-mix [88]
of the sample dropped by 40%.
The electrical resistivity had highest value at 0.02 wt% GO
GO/rGO Paste Wet-mix and rGO composites then it reduced as the concentration [93]
further increased.
When 1 wt% GNP is dispersed, the electrical resistance was
GNPs Mortar Wet-mix [106]
reduced from 300 kΩ to 19 kΩ.
The electrical resistivity showed a decrease of more than 1
GNP Mortar Wet-mix [111]
order of magnitude when 2.4 vol% GNP was added.
The introduction GNPs was confirmed to decrease the
GNP Paste Wet-mix electrical resistivity of cement paste from 18.85 kΩ·m to 6.26 [112]
kΩ·m.
The electrical resistivity of the cement composite sample was
decreased by 67.8% by adding graphene.
Bai et al. [43] measured the electrical conductivity of GRCCMs by the four-probe
method. The experiments showed that the electrical conductivity was related to the
distribution and concentration of the graphene fillers. As the graphene concentration
exceeded the percolation threshold, the water content and curing age had limited effects
on the electrical conductivity. Figure 21 shows the relationship between the electrical
resistivity of the GRCCMs and the volume fraction of graphene measured by using DC
(direct current) and AC (alternating current) methods [46]. When the graphene content was
smaller than the percolation threshold, i.e., 2 vol%, the separation between the neighboring
fillers was too far away and the graphene in the composites could not form a conductive
network. Therefore, the electrical resistivity was still relatively high. As the graphene
concentration further increased, the resistivity decreased.
tivity of the GRCCMs and the volume fraction of graphene measured by using DC (direct
current) and AC (alternating current) methods [46]. When the graphene content was
smaller than the percolation threshold, i.e., 2 vol%, the separation between the neighbor-
ing fillers was too far away and the graphene in the composites could not form a conduc-
Nanomaterials 2021, 11, 3220 tive network. Therefore, the electrical resistivity was still relatively high. As the graphene
19 of 31
concentration further increased, the resistivity decreased.
Figure21.
Figure Electricalresistivity
21.Electrical resistivityofofgraphene/cement
graphene/cement composites.Reprinted
composites. Reprinted withpermission
with permissionfrom
from
JinJin
et et
al.al.
[47][47] fabricated
fabricated a graphene-modified
a graphene-modified cementcement composite
composite and utilized
and utilized the elec-the
electrical conductivity of composites to develop a non-destructive method
trical conductivity of composites to develop a non-destructive method to monitor the pen- to monitor the
penetration of chloride ions in the concrete structure. Figure 22 shows
etration of chloride ions in the concrete structure. Figure 22 shows the conductive pathsthe conductive paths
formedbetween
formed betweengraphene
graphenefillers
fillersininthe
thecomposites.
composites.Their
Theirresults
resultsdemonstrated
demonstratedthat thatthe
the
electrical conductivity of the GRCCMs increased as the chloride concentration increased.
electrical conductivity of the GRCCMs increased as the chloride concentration increased.
Zhang et al. [53] developed a novel self-sensing cement composite by adding rGO. The
Zhang et al. [53] developed a novel self-sensing cement composite by adding rGO.
experiments indicated that the dispersion of the rGO increased the electrical conductivity
The experiments indicated that the dispersion of the rGO increased the electrical conduc-
by 23%. Goracci et al. [114] investigated the conduction mechanisms of GNP-reinforced
tivity by 23%. Goracci et al. [114] investigated the conduction mechanisms of GNP-rein-
CCMs. The reduction in electrical resistivity of the reinforced composites was attributed to
forced CCMs. The reduction in electrical resistivity of the reinforced composites was at-
the charge transport property and pore refinement by the addition of GNPs. Liu et al.’s [79]
Nanomaterials 2021, 11, 3220 tributed to the charge transport property and pore refinement by the addition of GNPs. 20 of 32
experiments showed that as the GNP concentration increased. The electrical resistance of
Liu et al.’s [79] experiments showed that as the GNP concentration increased. The electri-
the reinforcement CCMs had three zones, i.e., insulated, semi-conducted, and conducted
cal resistance of the reinforcement CCMs had three zones, i.e., insulated, semi-conducted,
zones. Sartipi et al. [74] studied the electrical resistivity of GO-reinforced CCMs. The bulk
and conducted
CCMs. The zones.
bulk Sartipiconductivity
electrical et al. [74] studied
of thethe electrical tested
sample resistivity of
14,GO-reinforced
electrical conductivity of the sample was tested at 7, 14, was
and 28 days.atIt7,was and 28 days.
evidenced thatIt
was evidenced that the addition of GO increased the electrical conductivity
the addition of GO increased the electrical conductivity of the sample. Rehman et al. [113] of the sample.
Rehman
found et al.
that with[113]
thefound that with the
incorporation incorporation
of graphene, the of graphene,
electrical the electrical
resistivity of CCMsresistivity
was
of CCMs was
decreased by updecreased
to 67.8%.by up to 67.8%.
Figure 22.
Figure 22. Formation
Formation of
of conductive
conductive paths
paths in
in cement
cement paste
pasteand
and GRCCMs.
GRCCMs. Reprinted
Reprintedwith
withpermission
permission
from Ref. [47]. Copyright 2017 Elsevier.
Sedaghatet
Sedaghat et al.
al. [30]
[30] investigated
investigated thethe electrical
electrical conductivity
conductivityofofGRCCMs
GRCCMs withwith different
different
grapheneconcentrations,
graphene concentrations,i.e.,
i.e.,0,0, 1 wt%,
1 wt%, 5 wt%,
5 wt%, and
and 1010 wt%.
wt%. They
They found
found a significant
a significant effect
effect of
of the graphene fillers on increasing the electrical conductivity of the composites. Du et al.
[115] reported that the change in electrical conductivity was greater than 1 order of mag-
nitude with and addition of 15 wt% GNPs. Bai et al. [69] experimentally investigated the
influences of silica fume concentration on electrical resistivity of the GRCCMs. Guo et al.
Figure 22. Formation of conductive paths in cement paste and GRCCMs. Reprinted with permission
Nanomaterials 2021, 11, 3220 Sedaghat et al. [30] investigated the electrical conductivity of GRCCMs with different 20 of 31
graphene concentrations, i.e., 0, 1 wt%, 5 wt%, and 10 wt%. They found a significant effect
of the graphene fillers on increasing the electrical conductivity of the composites. Du et al.
[115] reportedfillers
the graphene that the change in the
on increasing electrical conductivity
electrical conductivity was of greater than 1 order
the composites. Du etofal.mag-
[115]
nitude with and addition of 15 wt% GNPs. Bai et al. [69] experimentally investigated
reported that the change in electrical conductivity was greater than 1 order of magnitude with the
influences
and addition of 15 wt% GNPs. Bai et al. [69] experimentally investigated the influencesal.
of silica fume concentration on electrical resistivity of the GRCCMs. Guo et of
[112]
silicaprepared high-performance
fume concentration CCMs
on electrical by using
resistivity ofGNP as reinforcing
the GRCCMs. Guo fillers. It was
et al. [112] found
prepared
that the introduction
high-performance of GNPs
CCMs intoGNP
by using cement matrix reduced
as reinforcing fillers. the resistivity
It was of the
found that theCCMs from
introduction
18.85
of GNPskΩ·mintotocement
6.26 kΩ·m
matrix(as shown
reduced theinresistivity
Figure 23). The
of the increase
CCMs from in thekΩ
18.85 resistivity
·m to 6.26of kΩthe
·m
GRCCMs can significantly improve the sensitivity of the CCMs when they
(as shown in Figure 23). The increase in the resistivity of the GRCCMs can significantly improveare serving as
sensors for structural
the sensitivity healthwhen
of the CCMs monitoring.
they are serving as sensors for structural health monitoring.

Figure23.
Figure Variationof
23. Variation ofelectrical
electricalresistivity
resistivitywith
withtime.
time.Reprinted
Reprintedwith
withpermission
permissionfrom
fromRef.
Ref.[112].
[112].
Comparedto
Compared to experimental
experimentalwork, work,relatively
relativelyfewer
fewermodeling
modelingstudies
studieshave
havebeen
beenfound
found
for the electrical conductivity of GRCCMs. Le et al. [111] added GNP
for the electrical conductivity of GRCCMs. Le et al. [111] added GNP into the cement into the cement ma-
trix to prepare CCMs with electrical conductivity to quantify the material
matrix to prepare CCMs with electrical conductivity to quantify the material damage by damage by
measuring the change of electric potential. The authors used percolation
measuring the change of electric potential. The authors used percolation theory to study theory to study
the conductive
the conductivebehaviours
behavioursof ofGRCCMs.
GRCCMs.ItItwaswas found
found that
thatthe
the electrical
electricalconductivity
conductivityof ofthe
the
compositessuddenly
composites suddenlyincreased
increasedremarkably
remarkablywhen whenthethegraphene
grapheneconcentration
concentrationreached
reachedthethe
percolation threshold. Liu et al. [72] established a visual simulation model
percolation threshold. Liu et al. [72] established a visual simulation model as shown in as shown in
Figure 24 to analyze the percolation of GNP/cement composites. The percolation
Figure 24 to analyze the percolation of GNP/cement composites. The percolation threshold thresh-
old was
was foundfound
to beto2.2
bevol%
2.2 vol%
in theinsimulation.
the simulation.
Figure 24.
Figure 24. GNP/cement
GNP/cementcomposites
composites(a)
(a)Simulation model;
Simulation (b)(b)
model; Simulation result.
Simulation Reprinted
result. from
Reprinted Ref.
from
[72].[72].
Ref. Copyright 20182018
Copyright Elsevier
Elsevier.
Bai et al. [43] also employed percolation theory to study the conductivity of GRCCMs.
The percolation theory was validated by experimental results (as shown in Figure 25). It
was found that the percolation threshold did not depend on water/cement ratio. When
the graphene concentration was smaller than the percolation threshold, the curing time
had a considerable influence on the electrical conductivity of the composites. Once the
Figure 24. GNP/cement composites (a) Simulation model; (b) Simulation result. Reprinted from Ref.
[72]. Copyright 2018 Elsevier
Bai et al.
al. [43]
[43] also
alsoemployed
employedpercolation
percolation theory
theory toto study
studythetheconductivity
conductivity of ofGRCCMs.
GRCCMs.
The percolation theory was validated by experimental results (as shown in Figure 25). It
was found
found that
thatthethepercolation
percolationthreshold
threshold did
did notnot depend
depend on water/cement
on water/cement ratio.
ratio. When
When the
the graphene
graphene concentration
concentration was was smaller
smaller than than the percolation
the percolation threshold,
threshold, the curing
the curing timea
time had
had a considerable
considerable influence influence on the electrical
on the electrical conductivity
conductivity of the composites.
of the composites. Once the
Once the conductive
conductive
network was network
formed,was theformed, the curing
curing time time had
had a limited a limited
effect on theeffect on the
electrical electrical con-
conductivity. As
the graphene
ductivity. As content increased,
the graphene the influence
content increased,of the
water on the conductivity
influence of water on ofthethe composites
conductivity
increased.
of When the
the composites graphene
increased. concentration
When the graphenewasconcentration
smaller than thewaspercolation
smaller than threshold,
the per-
the wet-state
colation electrical
threshold, the conductivity was much
wet-state electrical higher than
conductivity themuch
was dry-state conductivity.
higher than the dry-As
the graphene
state concentration
conductivity. exceeded
As the graphene the percolation
concentration threshold,
exceeded the conductivity
the percolation of the
threshold,
dried composites
conductivity of thewas higher
dried than that
composites of the
was wet-state
higher composites.
than that of the wet-state composites.
Figure 25. Experimental

Experimental validation
validation of
of percolation
percolation theory.
theory. Reprinted
Reprinted with
with permission
permission from
from Ref.
Ref. [43].
[43].
Copyright
Copyright 2020
2020 Thmas
Thmas Telford Ltd.
Telford Ltd.
4. Piezoresistive Property
CCMs with piezoresistive properties have demonstrated great potential in developing
smart civil engineering structures with the capability of self-sensing and structural health
monitoring. For example, such CCMs with a piezoresistive property can be used in
buildings and infrastructures to monitor the strain and crack in the structures [116,117].
Therefore, the improvement in the piezoresistive property of the GRCCMs can significantly
enhance the sensitivity of such multifunctional composites as sensors.
It is evidenced that the electrical conductivity/resistivity possessed by GRCCMs
can vary with the deformation of the materials and structures. Extensive studies have
been done on the piezoresistive property of GRCCMs. Table 4 summarizes the work on
investigating the piezoelectrical properties of GRCCMs.
Table 4. Summary of studies on piezoelectrical properties of GRCCMs.
Filler Type Matrix Preparation Piezoelectrical Properties Ref.

For paste composites, the pressure sensitivity and strain sensitivity
were 2.52%/MPa and 363.10, respectively when the rGO
rGO Paste/Mortar Wet-mix concentration was 1.0 wt%. For mortar composites, the pressure [53]
sensitivity and strain sensitivity were 1.28%/MPa and 147.80,
respectively, when the rGO concentration was 2.00 wt%.
The mortar with 6.4 wt% GNPs had the best piezoresistive
GNPs Mortar Wet-mix [79]
performance.
Applying compressive loading, the resistivity value was reduced by
GNPs Concrete Wet-mix [81]
42%.
Table 4. Cont.
The largest strain sensitivity coefficient and stress reached up to

rGO Mortar Wet-mix [88]
1.28%/MPa and 147.80, respectively, with 2.00 wt% rGO.
The resistance of the GNP/cement composite monotonously
increased and decreased under cyclic compressive stress. The
GNPs Paste Wet-mix [112]
resistance could go back to the initial state when the pressure was
zero.
When the compressive strain was larger than 400 microstrain, the
GNP Mortar Wet-mix [118]
gauge factor was 100 after percolation.
Subjected to vertical compression, the electrical resistances in vertical,
GNP Mortar Wet-mix horizontal, and diagonal directions dropped by 5.5%, 1.8%, and 6.7%, [119]
respectively.
Wet- The increase of GNP concentration from 7.5 wt% to 10 wt%
GNP Mortar mix/Dry- deteriorated the gauge factor. There existed an optimum GNP [71]
mix concentration providing the best self-sensing properties.
Under maximum loading, the electrical resistance variation ratio was
Graphene Mortar Wet-mix [120]
2% and 25% for mesh and wire probes, respectively.
Du et al. [115] studied the piezoresistivity of CCMs incorporated with GNPs by

the four-probe testing method. A gauge factor in the order of magnitude of 102– 103
was obtained. It was found that the gauge factor increased with the increase of GNP
concentration at low strain. Such observation was attributed to the balance between
the contribution of the piezoresistivity from the matrix and the interface between matrix
and GNP fillers. Liu et al.’s [79] experiments investigated the piezoresistivity of GNP
and graphene oxide nanoplatelet (GONP) reinforced CCMs. GNPs were found to be
a better reinforcing filler than GONP and the cement mortar with a concentration of
6.4% GNP had better performance in the piezoresistive property. Rehman et al. [81]
tested the piezoresistive properties of GNP/cement composites to obtain the self-sensing
attribute. A drop of 42% in electrical resistivity of the composites was observed at the
maximum compressive load. This variation of the electrical resistivity with compression
was used for detecting damage and crack propagation in CCMs. Sun et al. [121] investigated
Nanomaterials 2021, 11, 3220 the piezoresistive properties of CCMs filled with nano graphite platelets. The electrical 23 of 32
response of the CCMs were subjected to cyclic compressive stress under different loading
conditions. Figure 26 shows the set up for testing the piezoresistivity of the composites. It
was found
without or that
withthe composite
a low withoutofor
concentration with
the a low concentration
reinforcements of unobvious
had no or the reinforcements
piezore-
had no effects.
sistive or unobvious piezoresistive
The composites witheffects. The composites
a concentration with
of 5 vol% a concentration
reinforcement hadofthe
5 vol%
most
reinforcement had the most
sensitive piezoresistivity. sensitive piezoresistivity.
Figure 26.
Figure 26. Sketch
Sketchofofmeasuring
measuringpiezoresistivity
piezoresistivityofof
GRCCMs. Reprinted
GRCCMs. with
Reprinted permission
with fromfrom
permission Ref.
Tao et al. [122] compared the performances of GNP- and CNT-reinforced CCMs. Fig-
ure 27 shows the change ratio of electrical resistivity and gauge factor with stress. The
cement composite sample containing 0.1% GNP (GNP-01) was found to have a more sig-
nificant change ratio of electrical resistivity and a larger gauge factor compared to the
other samples. This indicated that GNP-01 was more sensitive to stress and had a better
Figure 26. Sketch of measuring piezoresistivity of GRCCMs. Reprinted with permission from Ref.
Tao et al. [122] compared the performances of GNP- and CNT-reinforced CCMs.
Figure 27Taoshows
et al. [122] compared
the change the of
ratio performances of GNP- and
electrical resistivity andCNT-reinforced
gauge factor CCMs. Fig- The
with stress.
ure 27 shows the change ratio of electrical resistivity and gauge factor
cement composite sample containing 0.1% GNP (GNP-01) was found to have a more with stress. The
cement composite sample containing 0.1% GNP (GNP-01) was found to have a more sig-
significant change ratio of electrical resistivity and a larger gauge factor compared to the
nificant change ratio of electrical resistivity and a larger gauge factor compared to the
piezoresistive
piezoresistiveperformance.
performance.
FigureFigure 27. Piezoresistive

27. Piezoresistive results
results of cement
of cement composites:(a)
composites: (a) Fractional
Fractional change
changeratio of of
ratio electrical resistivity
electrical of GNP
resistivity and CNT
of GNP and CNT
reinforced samples; (b) Gauge factor of GNP and CNT reinforced samples. Reprinted with permission from Ref. [122].
reinforced samples; (b) Gauge factor of GNP and CNT reinforced samples. Reprinted with permission from Ref. [122].
Based on the analogy between electric field and the electrostatic field under anti-
Based
plane onloading,
shear the analogy
Pang between
et al. [118]electric
confirmedfield
theand the electrostatic
potential field under
for piezoresistive anti-plane
strain sens-
shear
ing of CCMs reinforced by GNPs. Guo et al. [112] prepared high-performance CCMs of
loading, Pang et al. [118] confirmed the potential for piezoresistive strain sensing byCCMs
reinforced by GNPs. Guo et al. [112] prepared high-performance CCMs
using GNP as reinforcing fillers. It was found with the introduction of GNPs into the ce- by using GNP as
reinforcing fillers.
ment matrix, It was found
the self-sensing with the introduction
performance of GNPs
of the composites into the
with 0.05% GNPscement matrix, the
was almost
self-sensing performance
doubled compared to of
thethe composites
composites with 0.05%
without GNPs.GNPs was
Pei et al.almost doubled compared
[110] prepared gra-
phene/PVA
to the compositeshybrid modified
without GNPs.CCMs Peiand their
et al. electrical
[110] and piezoelectric
prepared graphene/PVA properties
hybridweremodified
CCMssignificantly
and theirimproved
electricalwith
and apiezoelectric
low concentration of graphene
properties filler. Roopaimproved
were significantly et al. [123]with
de- a low
veloped smart cement composite sensors by using different kinds of conductive
concentration of graphene filler. Roopa et al. [123] developed smart cement composite sensors filler
(CNTs,different
by using CF, and kinds
graphene). The electromechanical
of conductive filler (CNTs, CF,examination of the fabricated
and graphene). sensor
The electromechanical
incited good strain sensing with respect to the applied load. Tao et al. [106] investigated
Nanomaterials 2021, 11, 3220 examination of the fabricated sensor incited good strain sensing with respect to the 24 ofapplied
32
the GNP reinforced CCMs. As shown in Figure 28, the piezoresistivity of the composites
load. Tao et al. [106] investigated the GNP reinforced CCMs. As shown in Figure 28, the
under cyclic compression was quantitatively evaluated by the four-probe method. Results
piezoresistivity of the composites under cyclic compression was quantitatively evaluated by the
four-probe
showed thatmethod. Results
the variation ofshowed thatconductivity
the electric the variationwith
of the
GNPelectric conductivity
concentration with aGNP
showed
concentration showed aThe
percolation behaviour. percolation behaviour.
piezoresistive The piezoresistive
attributes had very limitedattributes had very
dependence limited
on the
dependence
loading levelsonand
thethe
loading
GNP levels and the GNP
concentration. concentration.
The mechanisms The
that mechanisms
underpin that underpin
the piezoresis-
the
tivepiezoresistive
reaction werereaction were
attributed to attributed to the
the interfacial interfacial conductance
conductance between GNPs between GNPs and
and cement
cement matrix
matrix and anddeformation.
elastic elastic deformation.
Figure 28.
Figure 28. Schematic
Schematicdiagram
diagramofof
mechanisms
mechanismsforfor
piezoresistive responses
piezoresistive of GNP-modified
responses cement
of GNP-modified cement
composites. Reprinted with permission from Ref. [106]. Copyright 2019 Elsevier.
Compared to the plain cement sample, Zhu et al. ’s [77] study showed that the dis-
persion of graphene remarkably decreased the resistivity with enhanced pressure sensi-
tivity. The reinforced CCMs showed improved piezoresistivity when the graphene con-
centration was 0.05 compared to the case with 0.5 wt% graphene. Madbouly et al. [124]
Figure 28. Schematic diagram of mechanisms for piezoresistive responses of GNP-modified cement
Compared
Compared to the plainplain cement
cementsample,
sample,ZhuZhuetetal.al.’s’s[77]
[77]study
study showed
showed that
that thethe dis-
disper-
persion of graphene
sion of graphene remarkably
remarkably decreased
decreased the the resistivity
resistivity withwith enhanced
enhanced pressure
pressure sensi-
sensitivity.
tivity. The reinforced
The reinforced CCMs showed
CCMs showed improved improved piezoresistivity
piezoresistivity when thewhen the graphene
graphene con-
concentration
centration was 0.05tocompared
was 0.05 compared to the
the case with 0.5case
wt%with 0.5 wt%
graphene. graphene.
Madbouly Madbouly
et al. et al. [124]
[124] experimentally
experimentally explored theofpiezoresistivity
explored the piezoresistivity the GO reinforcedof the
CCMs.GO Basedreinforced
on theCCMs.
obtainedBased on the
results, the
composites
obtained could the
results, be efficiently
composites adopted
could asbepiezoresistive
efficiently adopted sensors.asApart from experiments,
piezoresistive sensors.
some theoretical
Apart work has
from experiments, been
some done on the
theoretical workpiezoresistive
has been done property of GRCCMs. Under
on the piezoresistive prop-
anti-plane
erty shear loading
of GRCCMs. Underusing the similarities
anti-plane between
shear loading using thethe2D similarities
electrostatic between
and electrostatic
the 2D
fields (as shown
electrostatic and in Figure 29),fields
electrostatic Le et al.
(as[111]
shown developed
in Figure a mathematical modeldeveloped
29), Le et al. [111] to correlate a
the damage extent
mathematical model toto
thecorrelate
change oftheelectrical
damageresistance.
extent to the Thechange
modelof was validated
electrical by their
resistance.
experimental
The model was results.
validated by their experimental results.
Figure
Figure 29.
29. Sketch
Sketch of
of damaged
damaged specimen
specimen with
with a notch. (a)
(a) Crack detection
detection with conductive
conductive plates
attached
attached to
to the
the ends
ends of
of the
the specimen;
specimen; (b)
(b) Mathematical
Mathematical analogy
analogy ofof anti-plane
anti-plane shear
shear applied
applied to
to the
the
ends of the specimen. Reprinted with permission from Ref. [111]. Copyright 2014 Elsevier.
ends of the specimen. Reprinted with permission from Ref. [111]. Copyright 2014 Elsevier.
5. Electromagnetic
5. Electromagnetic Property
Property
With the high
With high demand
demandfor forprotecting
protectingthe
thesensitive
sensitiveenvironment
environment from radiation
from hazards
radiation haz-
and wireless
ards communications,
and wireless communications, the electromagnetic
the electromagneticinterference (EMI)
interference properties
(EMI) of the
properties of
cement
the structure
cement is getting
structure is getting more
moreattention.
attention.Extensive
Extensiveresults
resultshave
have evidenced
evidenced that thethe
additionof
addition ofgraphene
graphenefillers
fillers into
into cement
cement materials
materials is a is a promising
promising methodmethod to develop
to develop mul-
tifunctional cement composite materials and structures with EMI attributes. Table Table
multifunctional cement composite materials and structures with EMI attributes. 5 sum-5
summarizes
marizes the work
the work on investigating
on investigating the electromagnetic
the electromagnetic properties
properties of GRCCMs.
of GRCCMs.
Table 5. Summary of studies on electromagnetic properties of GRCCMs.
Filler Type Matrix Preparation Electromagnetic Properties Ref.

Shielding effectiveness and wave absorption were increased by 1.6 and 7
times, respectively.
rGO Mortar Wet-mix Shielding effectiveness was improved by 45%. [53]
rGO Mortar Wet-mix Shielding effectiveness was increased by 30%~45%. [88]
GO Paste Dry-mix Shielding effectiveness could reach up to 46 dB. [125]
GO Mortar Wet-mix Shielding effectiveness was increased by 31%. [126]
Relative permittivity was increased by about 50% and 200% when the
GO Mortar Wet-mix [127]
frequency is in the ranges of 104 –5 × 106 Hz and 101 –103 Hz, respectively.
Within the range of 2–18 GHz, the average reflectivity loss was –8.2 dB
GNP Paste Wet-mix [128]
and the effective absorption bandwidth was as high as 4.4 GHz.
Within the range of 1–18 GHz, a minimum reflectivity of –14.7 dB was
rGO Paste Wet-mix achieved. An effective bandwidth of 14.4 GHz was achieved when the [129]
reflectivity was smaller than –5 dB.
GO Mortar Wet-mix Shielding effectiveness reached up to 40–50 dB. [130]
It was found that the contribution to the increase of shielding
effectiveness came from the absorption growth rather than reflection.
the effective absorption bandwidth was as high as 4.4 GHz.
Within the range of 1–18 GHz, a minimum reflectivity of –14.7 dB was
rGO Paste Wet-mix achieved. An effective bandwidth of 14.4 GHz was achieved when the [129]
reflectivity was smaller than –5 dB.
GO Mortar Wet-mix Shielding effectiveness reached up to 40–50 dB. [130]
It was found that the contribution to the increase of shielding effectiveness
came from the absorption growth rather than reflection.
Figure 30 shows the variation of the shielding effectiveness and reflectivity with the
frequency of GRCCMs by Sun et al. [46] It was was found
found that
that as
as the
the graphene
graphene filler
filler content
content
increased, the
increased, the shielding
shieldingeffectiveness
effectivenessofofthe
themodified
modifiedCCMs
CCMsincreased
increasedwhile
whilethe
thereflectivity
reflectiv-
decreased.
ity Compared
decreased. Comparedto plain cement,
to plain the shielding
cement, effectiveness
the shielding and and
effectiveness the reflectivity was
the reflectivity
increased by up to 1.6 and 7 times, respectively.
was increased by up to 1.6 and 7 times, respectively.
(a) (b)
Figure 30.
Figure 30. (a)
(a) Shielding
Shielding effectiveness and (b)
effectiveness and (b) Reflectivity of GRCCMs.
Reflectivity of GRCCMs. Reprinted
Reprinted with
with permission
permission from
from Ref.
Ref. [46].
[46]. Copyright
Copyright
2017 Elsevier.
2017 Elsevier.
Goracci et al. [114] investigated

investigated the the electromagnetic
electromagnetic properties
properties of of GNP-reinforced
GNP-reinforced
CCMs through dielectric
dielectric spectroscopy
spectroscopywithin
withinthe thefrequency
frequencyrange range1010−−2
2 Hz–10
Hz–1066 Hz. After
the addition of GNP, the the charge
charge transport
transport properties
properties werewere enhanced,
enhanced, and the electrical
electrical
capacitance had hadhigher
highervalues
values over
over all all
the the frequency
frequency ranges ranges involved.
involved. Sun etSun et al.added
al. [129] [129]
added
rGO, nanorGO,ferroferric
nano ferroferric
oxide, oxide,
and nanoandnickel
nano nickel particles
particles into the into the cement.
cement. With With
0.05%0.05%
rGO
added,
rGO the minimum
added, the minimum reflectivity of the of
reflectivity composite reached
the composite −14.7 dB
reached at 2.15
−14.7 dB atGHz.
2.15When
GHz.
the reflectivity
When is smaller
the reflectivity than −5than
is smaller dB, an−5effective bandwidth
dB, an effective of 14.4 GHz
bandwidth was GHz
of 14.4 achieved.
was
Chen et al.Chen
achieved. [126]etdispersed GO and CF
al. [126] dispersed GOinto andcement
CF into and foundand
cement thatfound
this combination
that this combi-was
more effective
nation was more in improving
effective inEMI shielding
improving than
EMI CF only. than
shielding WithCF 0.4only.
wt% GO-CF,
With 0.4a wt%shielding
GO-
Nanomaterials 2021, 11, 3220 effectiveness of 34 dB was achieved within the frequency range
CF, a shielding effectiveness of 34 dB was achieved within the frequency range 8.2–12.4 8.2–12.4 GHz, which26 of
was32
31% higher compared to the value with CF only. Singh et al. [125]
GHz, which was 31% higher compared to the value with CF only. Singh et al. [125] pre- prepared GO-ferrofluid-
cementGO-ferrofluid-cement
pared composites to test thecomposites
EMI effectiveness
to test thewithin
EMI the frequencywithin
effectiveness range the
8.2–12.4 GHz.
frequency
It is shown
range thatGHz.
8.2–12.4 the addition
It is shownof 30 wt%
that theGO and ferrofluid
addition of 30 wt% inGOthe and
cement matrixin
ferrofluid resulted
the ce-
in
menta shielding effectiveness
matrix resulted of 46 dB.effectiveness
in a shielding Cui et al.’s [132] of 46experiments
dB. Cui et al.’sdemonstrated that by
[132] experiments
adding 5% graphite platelets, the electromagnetic wave reflectivity
demonstrated that by adding 5% graphite platelets, the electromagnetic wave reflectivity of the composites was
decreased by 38% compared to pure CCMs. Long et al. [127] studied
of the composites was decreased by 38% compared to pure CCMs. Long et al. [127] stud- the combined effect
of
iedwaste cathode-ray
the combined tube
effect of (CRT)
waste and GO on mitigating
cathode-ray tube (CRT)electromagnetic interference
and GO on mitigating for
electro-
CCMs (as shown in Figure 31). The combined effect between
magnetic interference for CCMs (as shown in Figure 31). The combined effect between waste CRT glass and GO
significantly
waste CRT glass improved
and GO thesignificantly
permittivity.improved the permittivity.
Figure 31.
Figure 31. Relative
Relative permittivity
permittivity of
of cement
cement composites
composites with
with different
different GO
GO concentrations
concentrations within
within different
different frequency
frequency ranges
ranges
(a) 1–1022 Hz; (b) 102
2–1044 Hz; (c) 1044–5×106 Hz.
6 Reprinted with permission from Ref. [127]. Copyright 2019
(a) 1–10 Hz; (b) 10 –10 Hz; (c) 10 –5×10 Hz. Reprinted with permission from Ref. [127]. Copyright 2019 Elsevier.Elsevier.
Mazzoli et al. [130] dispersed GO and metallic fibers into a cement matrix and inves-
tigated the EMI shielding properties. It was found that the use of GO significantly im-
proved the EMI shielding effectiveness. Lv et al. [128] prepared CCMs reinforced with
Figure 31. Relative permittivity of cement composites with different GO concentrations within different frequency ranges
(a) 1–102 Hz; (b) 102–104 Hz; (c) 104–5×106 Hz. Reprinted with permission from Ref. [127]. Copyright 2019 Elsevier.
Mazzoli et
Mazzoli et al.
al. [130]
[130] dispersed
dispersedGO GOand andmetallic
metallicfibers
fibersinto
intoaacement
cementmatrix
matrixandandinvesti-
inves-
tigatedthe
gated the
EMI EMI shielding
shielding properties.
properties. It was
It was found
found that that theofuse
the use GOofsignificantly
GO significantly
improvedim-
proved
the EMI the EMI shielding
shielding effectiveness.
effectiveness. Lv etprepared
Lv et al. [128] al. [128] prepared CCMs reinforced
CCMs reinforced with GNP with and
GNP and
hollow hollow
glass glass microspheres
microspheres and examined and their
examined their electromagnetic
electromagnetic wave absorbing waveproperties.
absorbing
properties.
The reinforcedTheCCMs
reinforced CCMs had significantly
had significantly improved
improved absorbing absorbingWithin
properties. properties. Within
the range of
the range of 2–18 GHz, the average reflectivity loss was –8.2 dB and
2–18 GHz, the average reflectivity loss was –8.2 dB and the bandwidth was 4.4 GHz below the bandwidth was
4.4 GHz
–5 dB. Zhaobelow –5 dB.
et al. [131]Zhao et al. [131] experimentally
experimentally investigated the investigated
EMI propertiesthe EMI properties
of the prepared ofGO
the
prepared GO
reinforced CCMsreinforced CCMs
at 8.2–12.4 GHz.at 8.2–12.4
It was foundGHz. It was
that GO found
was that GO was
essential essential inEMI
in improving im-
proving EMI due
effectiveness effectiveness due to the
to the absorption of absorption of electromagnetic
electromagnetic radiation. et
radiation. Khushnood Khushnood
al.’s [133]
experimental results also demonstrated
et al.’s [133] experimental the effectiveness
results also demonstrated of enhancing
the effectiveness of the EMI properties
enhancing the EMI
through
properties dispersing
through graphene
dispersinginto a cement
graphene intomatrix. Phrompet
a cement matrix.etPhrompet
al. [31] investigated the di-
et al. [31] investi-
electric constant of rGO-reinforced CCMs (as shown in Figure 32). These
gated the dielectric constant of rGO-reinforced CCMs (as shown in Figure 32). These results results confirmed
that the reinforced
confirmed that theCCMs were effective
reinforced CCMs were in enhancing
effective dielectric properties,
in enhancing demonstrating
dielectric properties,
great potential as
demonstrating electromagnetic
great shielding material
potential as electromagnetic candidates.
shielding material candidates.
Figure 32. (a)

Figure 32. (a) Dielectric
Dielectric constant
constant and
and (b)
(b) dielectric
dielectric loss
loss of
of CCMs
CCMs with
with different
different concentrations
concentrations of
of rGO.
rGO. Reprinted
Reprinted with
with
6. Conclusions
In this review, the graphene fillers and the cement matrix used to develop high-
performance and multifunctional CCMs are firstly summarized. The advantages and
disadvantages of different graphene fillers and cement matrices are discussed. It was found
that compared to graphene, GO and rGO, GNP demonstrated great potential for practical
engineering application due to their comparative material properties with moderate cost
and availability for mass production. Methods/techniques, including TG/DTG/DSC,
FTIR, XPS, XRD, Raman spectroscopy, NMR, SEM, TEM, and FFM for characterizing
GRCCMs are introduced and discussed. Then the present study introduces experimental
and theoretical studies on three material properties of GRCCMs, i.e., electrical conductiv-
ity/resistivity, piezoresistivity, and electromagnetic interference. From the above review, it
is demonstrated that the dispersion of graphene fillers can increase the hydration process of
the composites and significantly improve the three material properties as involved in this
paper, which enable such modified CCM promises in developing self-sensing and smart
civil engineering materials and structures. However, there are still challenges in developing
GRCCMs. For example, more methods and work need to be explored for the good disper-
sion of graphene fillers into a cement matrix for large scale civil engineering structures.
Moreover, although extensive work has been done on graphene/cement composites, the
majority of the work is focused on experiments and very limited theoretical studies can
be found. Therefore, in the future, more theoretical work may need to be conducted for
a more comprehensive and deeper understanding of the mechanisms that underpin the
influences of graphene fillers on the material properties of the CCMs involved.
Author Contributions: Draft preparation, S.M.; data and resources collection, S.M., J.Y. and Y.W.;
Review and editing, J.Y. and C.F.; funding acquisition, C.F. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was supported by Innovative and Entrepreneurial Talents of Jiangsu Province
and Zhejiang Provincial Natural Science and Foundation under Grant No. LQY19E080001.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interests.
References
1. Gu, X.; Jin, X.; Zhou, Y. Basic Principles of Concrete Structures; Tongji University Press: Shanhhai, China; Springer: Cham,
Switzerland, 2016.
2. Han, B.; Zhang, L.; Ou, J. Smart and Multifunctional Concrete Toward Sustainable Infrastructures; Springer: Singapore, 2017.
3. Rendon Diaz Miron, L.E.; Lara, M.R. Concrete Durability: Cementitious Materials and Reinforced Concrete Properties, Behavior and
Corrosion Resistance; Springer: Cham, Switzerland, 2017.
4. Setareh, M.; Darvas, R. Concrete Structures; Springer: Cham, Switzerland, 2017.
5. Chiarello, M.; Zinno, R. Electrical conductivity of self-monitoring CFRC. Cem. Concr. Compos. 2005, 27, 463–469. [CrossRef]
6. Chen, B.; Wu, K.; Yao, W. Conductivity of carbon fiber reinforced cement-based composites. Cem. Concr. Compos. 2004, 26,
291–297. [CrossRef]
7. Han, B.; Guan, X.; Ou, J. Electrode design, measuring method and data acquisition system of carbon fiber cement paste
piezoresistive sensors. Sens. Actuator A-Phys. 2007, 135, 360–369. [CrossRef]
8. Wen, S.; Chung, D.D.L. Double percolation in the electrical conduction in carbon fiber reinforced cement-based materials. Carbon
2007, 45, 263–267. [CrossRef]
9. Yurdakul, A.; Dolekcekic, E.; Gunkaya, G.; Kavas, T.; Karasu, B. The usage of newly developed glass fibre in cement structure and
their characterization. Constr. Build. Mater. 2018, 170, 13–19. [CrossRef]
10. Chen, C.; Zhang, G.; Zornberg, J.G.; Morsy, A.M.; Huang, J. Interface bond behavior of tensioned glass fiber-reinforced polymer
(GFRP) tendons embedded in cemented soils. Constr. Build. Mater. 2020, 263, 120132. [CrossRef]
11. Li, H.; Xiao, H.; Ou, J. Effect of compressive strain on electrical resistivity of carbon black-filled cement-based composites. Cem.
Concr. Compos. 2006, 28, 824–828. [CrossRef]
12. Zhang, L.; Ding, S.; Han, B.; Yu, X.; Ni, Y.-Q. Effect of water content on the piezoresistive property of smart cement-based
materials with carbon nanotube/nanocarbon black composite filler. Compos. Appl. Sci. Manuf. 2019, 119, 8–20. [CrossRef]
13. Doo-Yeol, Y.; Ilhwan, Y.; Seung-Jung, L. Electrical Properties of Cement-Based Composites with Carbon Nanotubes, Graphene,
and Graphite Nanofibers. Sensors 2017, 17, 1064. [CrossRef]
14. Garcia-Macias, E.; D’Alessandro, A.; Castro-Triguero, R.; Perez-Mira, D.; Ubertini, F. Micromechanics modeling of the electrical
conductivity of carbon nanotube cement-matrix composites. Compos. B Eng. 2017, 108, 451–469. [CrossRef]
15. Wei, J.; Fan, Y.; Zhao, L.; Xue, F.; Hao, L.; Zhang, Q. Thermoelectric properties of carbon nanotube reinforced cement-based
composites fabricated by compression shear. Ceram. Int. 2018, 44, 5829–5833. [CrossRef]
16. Lee, C.; Wei, X.; Kysar, J.W.; Hone, J. Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene. Science
2008, 321, 385–388. [CrossRef]
17. Balandin, A.A.; Ghosh, S.; Bao, W.; Calizo, I.; Teweldebrhan, D.; Miao, F.; Lau, C.N. Superior Thermal Conductivity of Single-Layer
Graphene. Nano Lett. 2008, 8, 902–907. [CrossRef]
18. Du, X.; Skachko, I.; Barker, A.; Andrei, E.Y. Approaching ballistic transport in suspended graphene. Nat. Nanotechnol. 2008, 3,
491–495. [CrossRef] [PubMed]
19. Najafishad, S.; Manesh, H.D.; Zebarjad, S.M.; Hataf, N.; Mazaheri, Y. Production and investigation of mechanical properties and
electrical resistivity of cement-matrix nanocomposites with graphene oxide and carbon nanotube reinforcements. Arch. Civ. Mech.
Eng. 2020, 20, 57. [CrossRef]
20. Pisello, A.L.; D’Alessandro, A.; Sambuco, S.; Rallini, M.; Ubertini, F.; Asdrubali, F.; Materazzi, A.L.; Cotana, F. Multipurpose
experimental characterization of smart nanocomposite cement-based materials for thermal-energy efficiency and strain-sensing
capability. Sol. Energy Mater. Sol. Cells 2017, 161, 77–88. [CrossRef]
21. Lv, S.; Ting, S.; Liu, J.; Zhou, Q. Use of graphene oxide nanosheets to regulate the microstructure of hardened cement paste to
increase its strength and toughness. CrystEngComm 2014, 16, 8508–8516. [CrossRef]
22. Horszczaruk, E.; Mijowska, E.; Kalenczuk, R.J.; Aleksandrzak, M.; Mijowska, S. Nanocomposite of cement/graphene oxide–
Impact on hydration kinetics and Young’s modulus. Constr. Build. Mater. 2015, 78, 234–242. [CrossRef]
23. Pan, Z.; He, L.; Qiu, L.; Korayem, A.H.; Li, G.; Zhu, J.W.; Collins, F.; Li, D.; Duan, W.H.; Wang, M.C. Mechanical properties and
microstructure of a graphene oxide–cement composite. Cem. Concr. Compos. 2015, 58, 140–147. [CrossRef]
24. Cao, M.-l.; Zhang, H.-X.; Zhang, C. Effect of graphene on mechanical properties of cement mortars. J. Cent. South Univ. 2016, 23,
919–925. [CrossRef]
25. Li, X.; Korayem, A.H.; Li, C.; Liu, Y.; He, H.; Sanjayan, J.G.; Duan, W.H. Incorporation of graphene oxide and silica fume into
cement paste: A study of dispersion and compressive strength. Constr. Build. Mater. 2016, 123, 327–335. [CrossRef]
26. Wang, B.; Jiang, R.; Wu, Z. Investigation of the Mechanical Properties and Microstructure of Graphene Nanoplatelet-Cement
Composite. Nanomaterials 2016, 6, 200. [CrossRef]
27. Li, X.; Lu, Z.; Chuah, S.; Li, W.; Liu, Y.; Duan, W.H.; Li, Z. Effects of graphene oxide aggregates on hydration degree, sorptivity,
and tensile splitting strength of cement paste. Compos. A Appl. Sci. Manuf. 2017, 100, 1–8. [CrossRef]
28. Mokhtar, M.M.; Abo-El-Enein, S.A.; Hassaan, M.Y.; Morsy, M.S.; Khalil, M.H. Mechanical performance, pore structure and
micro-structural characteristics of graphene oxide nano platelets reinforced cement. Constr. Build. Mater. 2017, 138, 333–339.
[CrossRef]
29. Jing, G.; Ye, Z.; Wu, J.; Wang, S.; Cheng, X.; Strokova, V.; Nelyubova, V. Introducing reduced graphene oxide to enhance the
thermal properties of cement composites. Cem. Concr. Compos. 2020, 109, 103559. [CrossRef]
30. Sedaghat, A.; Ram, M.K.; Zayed, A.; Kamal, R.; Shanahan, N. Investigation of physical properties of graphene-cement composite
for structural applications. Open J. Compos. Mater. 2014, 4, 12–21. [CrossRef]
31. Phrompet, C.; Sriwong, C.; Ruttanapun, C. Mechanical, dielectric, thermal and antibacterial properties of reduced graphene oxide
(rGO)-nanosized C3AH6 cement nanocomposites for smart cement-based materials. Compos. B Eng. 2019, 175, 107128. [CrossRef]
32. Chintalapudi, K.; Pannem, R.M.R. Enhanced Strength, Microstructure, and Thermal properties of Portland Pozzolana Fly
ash-based cement composites by reinforcing Graphene Oxide nanosheets. J. Build. Eng. 2021, 42, 102521. [CrossRef]
33. Al-Dahawi, A.; Sarwary, M.H.; Öztürk, O.; Yıldırım, G.; Akın, A.; Şahmaran, M.; Lachemi, M. Electrical percolation threshold of
cementitious composites possessing self-sensing functionality incorporating different carbon-based materials. Smart Mater. Struct.
2016, 25, 105005. [CrossRef]
34. Xu, J.; Zhang, D. Pressure-sensitive properties of emulsion modified graphene nanoplatelets/cement composites. Cem. Concr.
Compos. 2017, 84, 74–82. [CrossRef]
35. ˛ M.; Pichór, W. Piezoresistive properties of cement composites with expanded graphite. Compos. Commun. 2020, 19, 99–102.
Frac,
[CrossRef]
36. Bianco, A.; Cheng, H.-M.; Enoki, T.; Gogotsi, Y.; Hurt, R.H.; Koratkar, N.; Kyotani, T.; Monthioux, M.; Park, C.R.; Tascon, J.M.D.;
et al. All in the graphene family–A recommended nomenclature for two-dimensional carbon materials. Carbon 2013, 65, 1–6.
[CrossRef]
37. Wick, P.; Louw-Gaume, A.E.; Kucki, M.; Krug, H.F.; Kostarelos, K.; Fadeel, B.; Dawson, K.A.; Salvati, A.; Vázquez, E.; Ballerini, L.;
et al. Classification Framework for Graphene-Based Materials. Angew. Chem. Int. Ed. 2014, 53, 7714–7718. [CrossRef]
38. Sreeja, K.; Naresh Kumar, T. Effect of graphene oxide on fresh, hardened and mechanical properties of cement mortar. Mater.
Today Proc. 2021, 46, 2235–2239. [CrossRef]
39. Jiang, Z.; Sevim, O.; Ozbulut, O.E. Mechanical properties of graphene nanoplatelets-reinforced concrete prepared with different
dispersion techniques. Constr. Build. Mater. 2021, 303, 124472. [CrossRef]
40. Feng, C.; Zhu, D.; Wang, Y.; Jin, S. Electromechanical Behaviors of Graphene Reinforced Polymer Composites: A Review. Materials
2020, 13, 528. [CrossRef]
41. Folorunso, O.; Hamam, Y.; Sadiku, R.; Ray, S.S.; Adekoya, G.J. Synthesis methods of borophene, graphene-loaded polypyrrole
nanocomposites and their benefits for energy storage applications: A brief overview. FlatChem 2021, 26, 100211. [CrossRef]
42. Ho, V.D.; Ng, C.-T.; Coghlan, C.J.; Goodwin, A.; Mc Guckin, C.; Ozbakkaloglu, T.; Losic, D. Electrochemically produced graphene
with ultra large particles enhances mechanical properties of Portland cement mortar. Constr. Build. Mater. 2020, 234, 117403.
[CrossRef]
43. Bai, S.; Jiang, L.; Jiang, Y.; Jin, M.; Jiang, S.; Tao, D. Research on electrical conductivity of graphene/cement composites. Adv. Cem.
Res. 2020, 32, 45–52. [CrossRef]
44. Liu, J.; Fu, J.; Yang, Y.; Gu, C. Study on dispersion, mechanical and microstructure properties of cement paste incorporating
graphene sheets. Constr. Build. Mater. 2019, 199, 1–11. [CrossRef]
45. Hou, D.; Lu, Z.; Li, X.; Ma, H.; Li, Z. Reactive molecular dynamics and experimental study of graphene-cement composites:
Structure, dynamics and reinforcement mechanisms. Carbon 2017, 115, 188–208. [CrossRef]
46. Sun, S.; Ding, S.; Han, B.; Dong, S.; Yu, X.; Zhou, D.; Ou, J. Multi-layer graphene-engineered cementitious composites with
multifunctionality/intelligence. Compos. B Eng. 2017, 129, 221–232. [CrossRef]
47. Jin, M.; Jiang, L.; Lu, M.; Bai, S. Monitoring chloride ion penetration in concrete structure based on the conductivity of
graphene/cement composite. Constr. Build. Mater. 2017, 136, 394–404. [CrossRef]
48. Yu, L.; Wu, R. Using graphene oxide to improve the properties of ultra-high-performance concrete with fine recycled aggregate.
Constr. Build. Mater. 2020, 259, 120657. [CrossRef]
49. Zhang, Y.; Yang, T.; Jia, Y.; Hou, D.; Li, H.; Jiang, J.; Zhang, J. Molecular dynamics study on the weakening effect of moisture
content on graphene oxide reinforced cement composite. Chem. Phys. Lett. 2018, 708, 177–182. [CrossRef]
50. Fan, D.; Lue, L.; Yang, S. Molecular dynamics study of interfacial stress transfer in graphene-oxide cementitious composites.
Comput. Mat. Sci. 2017, 139, 56–64. [CrossRef]
51. Wang, M.; Wang, R.M.; Yao, H.; Wang, Z.J.; Zheng, S.R. Adsorption characteristics of graphene oxide nanosheets on cement. RSC
Adv. 2016, 6, 63365–63372. [CrossRef]
52. Gholampour, A.; Valizadeh Kiamahalleh, M.; Tran, D.N.; Ozbakkaloglu, T.; Losic, D. From graphene oxide to reduced graphene
oxide: Impact on the physiochemical and mechanical properties of graphene–cement composites. ACS Appl. Mater. Interfaces
2017, 9, 43275–43286. [CrossRef] [PubMed]
53. Zhang, N.; She, W.; Du, F.; Xu, K. Experimental Study on Mechanical and Functional Properties of Reduced Graphene Ox-
ide/Cement Composites. Materials 2020, 13, 3015. [CrossRef]
54. Zohhadi, N.; Aich, N.; Matta, F.; Saleh, N.B.; Ziehl, P. Graphene Nanoreinforcement for Cement Composites. Nanotechnol. Constr.
2015, 265–270. [CrossRef]
55. Wang, B.; Deng, S. Effect and mechanism of graphene nanoplatelets on hydration reaction, mechanical properties and microstruc-
ture of cement composites. Constr. Build. Mater. 2019, 228, 116720. [CrossRef]
56. Wang, B.; Shuang, D. Effect of graphene nanoplatelets on the properties, pore structure and microstructure of cement composites.
Mater. Express 2018, 8, 407–416. [CrossRef]
57. Gong, K.; Pan, Z.; Korayem, A.H.; Qiu, L.; Li, D.; Collins, F.; Wang, C.M.; Duan, W.H. Reinforcing effects of graphene oxide on
portland cement paste. J. Mater. Civ. Eng. 2015, 27, A4014010. [CrossRef]
58. Li, W.; Li, X.; Chen, S.J.; Liu, Y.M.; Duan, W.H.; Shah, S.P. Effects of graphene oxide on early-age hydration and electrical resistivity
of Portland cement paste. Constr. Build. Mater. 2017, 136, 506–514. [CrossRef]
59. Zhu, X.; Kang, X.; Deng, J.; Yang, K.; Yu, L.; Yang, C. A comparative study on shrinkage characteristics of graphene oxide (GO)
and graphene nanoplatelets (GNPs) modified alkali-activated slag cement composites. Mater. Struct. 2021, 54, 106. [CrossRef]
60. Zhu, X.H.; Kang, X.J.; Yang, K.; Yang, C.H. Effect of graphene oxide on the mechanical properties and the formation of layered
double hydroxides (LDHs) in alkali-activated slag cement. Constr. Build. Mater. 2017, 132, 290–295. [CrossRef]
61. Wang, Q.; Cui, X.; Wang, J.; Li, S.; Lv, C.; Dong, Y. Effect of fly ash on rheological properties of graphene oxide cement paste.
Constr. Build. Mater. 2017, 138, 35–44. [CrossRef]
62. Sharma, S.; Arora, S. Economical graphene reinforced fly ash cement composite made with recycled aggregates for improved
sulphate resistance and mechanical performance. Constr. Build. Mater. 2018, 162, 608–612. [CrossRef]
63. Wang, Q.; Li, S.; Pan, S.; Cui, X.; Corr, D.J.; Shah, S.P. Effect of graphene oxide on the hydration and microstructure of fly
ash-cement system. Constr. Build. Mater. 2019, 198, 106–119. [CrossRef]
64. Saafi, M.; Tang, L.; Fung, J.; Rahman, M.; Liggat, J. Enhanced properties of graphene/fly ash geopolymeric composite cement.
Cem. Concr. Res. 2015, 67, 292–299. [CrossRef]
65. Lauermannová, A.-M.; Antončík, F.; Lojka, M.; Jankovský, O.; Pavlíková, M.; Pivák, A.; Záleská, M.; Pavlík, Z. The Impact of
Graphene and Diatomite Admixtures on the Performance and Properties of High-Performance Magnesium Oxychloride Cement
Composites. Materials 2020, 13, 5708. [CrossRef]
66. Liu, Y.; Jia, M.; Song, C.; Lu, S.; Wang, H.; Zhang, G.; Yang, Y. Enhancing ultra-early strength of sulphoaluminate cement-based
materials by incorporating graphene oxide. Nanotechnol. Rev. 2020, 9, 17–27. [CrossRef]
67. Ma, W.; Zhang, D. Multifunctional structural supercapacitor based on graphene and magnesium phosphate cement. J. Compos.
Mater. 2018, 53, 719–730. [CrossRef]
68. Lu, Z.; Hou, D.; Ma, H.; Fan, T.; Li, Z. Effects of graphene oxide on the properties and microstructures of the magnesium
potassium phosphate cement paste. Constr. Build. Mater. 2016, 119, 107–112. [CrossRef]
69. Bai, S.; Jiang, L.; Xu, N.; Jin, M.; Jiang, S. Enhancement of mechanical and electrical properties of graphene/cement composite
due to improved dispersion of graphene by addition of silica fume. Constr. Build. Mater. 2018, 164, 433–441. [CrossRef]
70. Shamsaei, E.; de Souza, F.B.; Yao, X.; Benhelal, E.; Akbari, A.; Duan, W. Graphene-based nanosheets for stronger and more durable
concrete: A review. Constr. Build. Mater. 2018, 183, 642–660. [CrossRef]
71. Ozbulut, O.E.; Jiang, Z.; Harris, D.K. Exploring scalable fabrication of self-sensing cementitious composites with graphene
nanoplatelets. Smart Mater. Struct. 2018, 27, 115029. [CrossRef]
72. Liu, Y.; Wang, M.; Wang, W. Electric induced curing of graphene/cement-based composites for structural strength formation in
deep-freeze low temperature. Mater. Des. 2018, 160, 783–793. [CrossRef]
73. Li, G.; Zhang, L.W. Microstructure and phase transformation of graphene-cement composites under high temperature. Compos. B
Eng. 2019, 166, 86–94. [CrossRef]
74. Sartipi, F.; Institute of Construction Materials; Gharizadeh, A.; Gamil, M. Western Sydney University Electrical resistance of
graphene reinforced cement paste. J. Constr. Mater. 2019, 1. [CrossRef]
75. Ghosh, S.; Harish, S.; Rocky, K.A.; Ohtaki, M.; Saha, B.B. Graphene enhanced thermoelectric properties of cement based
composites for building energy harvesting. Energy Build. 2019, 202, 109419. [CrossRef]
76. Al-Dahawi, A.; Öztürk, O.; Emami, F.; Yıldırım, G.; Şahmaran, M. Effect of mixing methods on the electrical properties of
cementitious composites incorporating different carbon-based materials. Constr. Build. Mater. 2016, 104, 160–168. [CrossRef]
77. Zhu, S.; Qin, X.; Zou, Z.; Zhang, R.; Jiang, Y. Preparation and evaluation of surfactant-stabilized graphene sheets and piezoresis-
tivity of GPs/cement composite. Carbon Lett. 2019, 30, 93–98. [CrossRef]
78. Prabavathy, S.; Jeyasubramanian, K.; Prasanth, S.; Hikku, G.S.; Robert, R.B.J. Enhancement in behavioral properties of cement
mortar cubes admixed with reduced graphene oxide. J. Build. Eng. 2020, 28, 101082. [CrossRef]
79. Liu, Q.; Xu, Q.; Yu, Q.; Gao, R.; Tong, T. Experimental investigation on mechanical and piezoresistive properties of cementitious
materials containing graphene and graphene oxide nanoplatelets. Constr. Build. Mater. 2016, 127, 565–576. [CrossRef]
80. Akarsh, P.K.; Marathe, S.; Bhat, A.K. Influence of graphene oxide on properties of concrete in the presence of silica fumes and
M-sand. Constr. Build. Mater. 2020, 268, 121093. [CrossRef]
81. Rehman, S.K.U.; Ibrahim, Z.; Memon, S.A.; Javed, M.F.; Khushnood, R.A. A Sustainable Graphene Based Cement Composite.
Sustainability 2017, 9, 1229. [CrossRef]
82. Li, X.; Wang, L.; Liu, Y.; Li, W.; Dong, B.; Duan, W.H. Dispersion of graphene oxide agglomerates in cement paste and its effects
on electrical resistivity and flexural strength. Cem. Concr. Compos. 2018, 92, 145–154. [CrossRef]
83. Zhao, L.; Guo, X.; Liu, Y.; Ge, C.; Chen, Z.; Guo, L.; Shu, X.; Liu, J. Investigation of dispersion behavior of GO modified by
different water reducing agents in cement pore solution. Carbon 2018, 127, 255–269. [CrossRef]
84. Wang, B.; Pang, B. Mechanical property and toughening mechanism of water reducing agents modified graphene nanoplatelets
reinforced cement composites. Constr. Build. Mater. 2019, 226, 699–711. [CrossRef]
85. Zhao, L.; Guo, X.; Ge, C.; Li, Q.; Guo, L.; Shu, X.; Liu, J. Mechanical behavior and toughening mechanism of polycarboxylate
superplasticizer modified graphene oxide reinforced cement composites. Compos. Part B Eng. 2017, 113, 308–316. [CrossRef]
86. Chuah, S.; Li, W.; Chen, S.J.; Sanjayan, J.G.; Duan, W.H. Investigation on dispersion of graphene oxide in cement composite using
different surfactant treatments. Constr. Build. Mater. 2018, 161, 519–527. [CrossRef]
87. Babak, F.; Abolfazl, H.; Alimorad, R.; Parviz, G. Preparation and Mechanical Properties of Graphene Oxide: Cement Nanocom-
posites. Sci. World J. 2014, 2014, 276323. [CrossRef] [PubMed]
88. Zhai, S.; Pang, B.; Liu, G.; Zhang, Y.; Xu, K.; She, W.; Zhang, Y. Investigation on preparation and multifunctionality of reduced
graphene oxide cement mortar. Constr. Build. Mater. 2021, 275, 122119. [CrossRef]
89. Ma, J.; Zhao, H.; Shang, Y.; Peng, C.; Liu, H.; Zheng, S.; Wang, T.; Qi, S.; Ran, Q. Synthesis of a small molecular polydentate
polymer IHP-MP and its application to cement or graphene oxide dispersion via strong interactions between adsorption groups
and interfaces. J. Mat. Sci. 2020, 55, 4701–4716. [CrossRef]
90. Li, Q.; He, C.; Zhou, H.; Xie, Z.; Li, D. Effects of polycarboxylate superplasticizer-modified graphene oxide on hydration
characteristics and mechanical behavior of cement. Constr. Build. Mater. 2021, 272, 121904. [CrossRef]
91. Wang, M.; Yao, H. Comparison Study on the Adsorption Behavior of Chemically Functionalized Graphene Oxide and Graphene
Oxide on Cement. Materials 2020, 13, 3274. [CrossRef]
92. Wang, M.; Yao, H.; Wang, R.; Zheng, S. Chemically functionalized graphene oxide as the additive for cement–matrix composite
with enhanced fluidity and toughness. Constr. Build. Mater. 2017, 150, 150–156. [CrossRef]
93. Qureshi, T.S.; Panesar, D.K. Impact of graphene oxide and highly reduced graphene oxide on cement based composites. Constr.
Build. Mater. 2019, 206, 71–83. [CrossRef]
94. Kashif Ur Rehman, S.; Ibrahim, Z.; Memon, S.A.; Aunkor, M.T.H.; Faisal, J.M.; Mehmood, K.; Shah, S.M.A. Influence of Graphene
Nanosheets on Rheology, Microstructure, Strength Development and Self-Sensing Properties of Cement Based Composites.
Sustainability 2018, 10, 822. [CrossRef]
95. Wang, L.; Li, Q.; Song, J.; Liu, S. Effect of graphene oxide on early hydration and compressive strength of Portland cement-copper
tailing powder composite binder. Powder Technol. 2021, 386, 428–436. [CrossRef]
96. Wang, M.; Wang, R.; Yao, H.; Farhan, S.; Zheng, S.; Du, C. Study on the three dimensional mechanism of graphene oxide
nanosheets modified cement. Constr. Build. Mater. 2016, 126, 730–739. [CrossRef]
97. Wang, Y.; Yang, J.; Ouyang, D. Effect of graphene oxide on mechanical properties of cement mortar and its strengthening
mechanism. Materials 2019, 12, 3753. [CrossRef]
98. Yaseen, S.A.; Yiseen, G.A.; Li, Z. Elucidation of Calcite Structure of Calcium Carbonate Formation Based on Hydrated Cement
Mixed with Graphene Oxide and Reduced Graphene Oxide. ACS Omega 2019, 4, 10160–10170. [CrossRef]
99. Yang, H.; Monasterio, M.; Cui, H.; Han, N. Experimental study of the effects of graphene oxide on microstructure and properties
of cement paste composite. Compos. Part A Appl. Sci. Manuf. 2017, 102, 263–272. [CrossRef]
100. Xu, G.; Du, S.; He, J.; Shi, X. The role of admixed graphene oxide in a cement hydration system. Carbon 2019, 148, 141–150.
[CrossRef]
101. Kang, X.; Zhu, X.; Qian, J.; Liu, J.; Huang, Y. Effect of graphene oxide (GO) on hydration of tricalcium silicate (C3S). Constr. Build.
Mater. 2019, 203, 514–524. [CrossRef]
102. Murugan, M.; Santhanam, M.; Gupta, S.S.; Pradeep, T.; Shah, S.P. Influence of 2D rGO nanosheets on the properties of OPC paste.
Cem. Concr. Compos. 2016, 70, 48–59. [CrossRef]
103. Du, H.; Gao, H.J.; Pang, S.D. Improvement in concrete resistance against water and chloride ingress by adding graphene
nanoplatelet. Cem. Concr. Res. 2016, 83, 114–123. [CrossRef]
104. Du, H.; Pang, S.D. Enhancement of barrier properties of cement mortar with graphene nanoplatelet. Cem. Concr. Res. 2015, 76,
10–19. [CrossRef]
105. Du, H.; Pang, S.D. Dispersion and stability of graphene nanoplatelet in water and its influence on cement composites. Constr.
Build. Mater. 2018, 167, 403–413. [CrossRef]
106. Tao, J.; Wang, X.; Wang, Z.; Zeng, Q. Graphene nanoplatelets as an effective additive to tune the microstructures and piezoresistive
properties of cement-based composites. Constr. Build. Mater. 2019, 209, 665–678. [CrossRef]
107. Jing, G.; Wu, J.; Lei, T.; Wang, S.; Strokova, V.; Nelyubova, V.; Wang, M.; Ye, Z. From graphene oxide to reduced graphene oxide:
Enhanced hydration and compressive strength of cement composites. Constr. Build. Mater. 2020, 248, 118699. [CrossRef]
108. Alkhateb, H.; Al-Ostaz, A.; Cheng, A.H.-D.; Li, X. Materials Genome for Graphene-Cement Nanocomposites. J. Nanomech.
Micromech. 2013, 3, 67–77. [CrossRef]
109. Tong, T.; Fan, Z.; Liu, Q.; Wang, S.; Tan, S.; Yu, Q. Investigation of the effects of graphene and graphene oxide nanoplatelets on the
micro- and macro-properties of cementitious materials. Constr. Build. Mater. 2015, 106, 102–114. [CrossRef]
110. Pei, C.; Ueda, T.; Zhu, J. Investigation of the effectiveness of graphene/polyvinyl alcohol on the mechanical and electrical
properties of cement composites. Mater. Struct. 2020, 53, 66. [CrossRef]
111. Le, J.-L.; Du, H.; Dai Pang, S. Use of 2D Graphene Nanoplatelets (GNP) in cement composites for structural health evaluation.
Compos. B Eng. 2014, 67, 555–563. [CrossRef]
112. Guo, L.; Wu, J.; Wang, H. Mechanical and perceptual characterization of ultra-high-performance cement-based composites with
silane-treated graphene nano-platelets. Constr. Build. Mater. 2019, 240, 117926. [CrossRef]
113. Rehman, S.K.U.; Ibrahim, Z.; Jameel, M.; Memon, S.A.; Javed, M.F.; Aslam, M.; Mehmood, K.; Nazar, S. Assessment of Rheological
and Piezoresistive Properties of Graphene based Cement Composites. Int. J. Concr. Struct. Mater. 2018, 12, 64. [CrossRef]
114. Goracci, G.S.; Dolado, J. Elucidation of Conduction Mechanism in Graphene Nanoplatelets (GNPs)/Cement Composite Using
Dielectric Spectroscopy. Materials 2020, 13, 275. [CrossRef]
115. Du, H.; Quek, S.T.; Dai Pang, S. Smart multifunctional cement mortar containing graphite nanoplatelet. In Sensors and Smart
Structures Technologies for Civil, Mechanical, and Aerospace Systems; International Society for Optics and Photonics: San Diego, CA,
USA, 2013.
116. Wu, Z.; Wei, J.; Dong, R.; Chen, H. Epoxy Composites with Reduced Graphene Oxide-Cellulose Nanofiber Hybrid Filler and
Their Application in Concrete Strain and Crack Monitoring. Sensors 2019, 19, 3963. [CrossRef]
117. Ghosh, S.; Harish, S.; Ohtaki, M.; Saha, B.B. Thermoelectric figure of merit enhancement in cement composites with graphene and
transition metal oxides. Mater. Today Energy 2020, 18, 100492. [CrossRef]
118. Dai Pang, S.; Gao, H.J.; Xu, C.; Quek, S.T.; Du, H. Strain and damage self-sensing cement composites with conductive graphene
nanoplatelet. In Sensors and Smart Structures Technologies for Civil, Mechanical, and Aerospace Systems; International Society for
Optics and Photonics: San Diego, CA, USA, 2014.
119. Liu, Q.; Gao, R.; Tam, V.W.Y.; Li, W.; Xiao, J. Strain monitoring for a bending concrete beam by using piezoresistive cement-based
sensors. Constr. Build. Mater. 2018, 167, 338–347. [CrossRef]
120. Zhang, Y.; Wen-Xin, W.; Qiong, L. Experimental Study on the Influence of Different Types of Probes on Piezoresistive Characteris-
tics of Smart Concrete In-filled with Graphene. DEStech Trans. Mater. Sci. Eng. 2017. [CrossRef]
121. Sun, S.; Han, B.; Jiang, S.; Yu, X.; Wang, Y.; Li, H.; Ou, J. Nano graphite platelets-enabled piezoresistive cementitious composites
for structural health monitoring. Constr. Build. Mater. 2017, 136, 314–328. [CrossRef]
122. Tao, J.; Wang, J.; Zeng, Q. A comparative study on the influences of CNT and GNP on the piezoresistivity of cement composites.
Mater. Lett. 2019, 259, 126858. [CrossRef]
123. Roopa, A.K.; Hunashyal, A.M.; Venkaraddiyavar, P.; Ganachari, S.V. Smart hybrid nano composite concrete embedded sensors
for structural health monitoring. Mater. Today Proc. 2020, 27, 603–609. [CrossRef]
124. Madbouly, A.I.; Mokhtar, M.M.; Morsy, M.S. Evaluating the performance of rGO/cement composites for SHM applications.
Constr. Build. Mater. 2020, 250, 118841. [CrossRef]
125. Singh, A.P.; Mishra, M.; Chandra, A.; Dhawan, S. Graphene oxide/ferrofluid/cement composites for electromagnetic interference
shielding application. Nanotechnology 2011, 22, 465701. [CrossRef]
126. Chen, J.; Zhao, D.; Ge, H.; Wang, J. Graphene oxide-deposited carbon fiber/cement composites for electromagnetic interference
shielding application. Constr. Build. Mater. 2015, 84, 66–72. [CrossRef]
127. Long, W.-J.; Gu, Y.-C.; Ma, H.; Li, H.-D.; Xing, F. Mitigating the electromagnetic radiation by coupling use of waste cathode-ray
tube glass and graphene oxide on cement composites. Compos. Part B Eng. 2018, 168, 25–33. [CrossRef]
128. Lv, X.; Duan, Y.; Chen, G. Electromagnetic wave absorption properties of cement-based composites filled with graphene
nano-platelets and hollow glass microspheres. Constr. Build. Mater. 2017, 162, 280–285. [CrossRef]
129. Sun, Y.F.; Zhou, T.S.; Gao, P.W.; Chen, M.; Liu, H.W.; Xun, Y. Microstructure and Microwave Absorption Properties of Cement-
Based Material Reinforced with Reduced Graphene Oxide and Nanoparticles. Strength Mater. 2019, 51, 601–608. [CrossRef]
130. Mazzoli, A.; Corinaldesi, V.; Donnini, J.; Di Perna, C.; Micheli, D.; Vricella, A.; Pastore, R.; Bastianelli, L.; Moglie, F.; Mariani
Primiani, V. Effect of graphene oxide and metallic fibers on the electromagnetic shielding effect of engineered cementitious
composites. J. Build. Eng. 2018, 18, 33–39. [CrossRef]
131. Zhao, D.; Chen, J.; Gao, Q.; Ge, H.Y. Graphene Oxide/Cement Composites for Electromagnetic Interference Shielding. Mater. Sci.
Forum 2014, 809-810, 485–489. [CrossRef]
132. Cui, X.; Sun, S.; Han, B.; Yu, X.; Ouyang, J.; Zeng, S.; Ou, J. Mechanical, thermal and electromagnetic properties of nanographite
platelets modified cementitious composites. Compos. Part A Appl. Sci. Manuf. 2017, 93, 49–58. [CrossRef]
133. Khushnood, R.A.; Ahmad, S.; Savi, P.; Tulliani, J.-M.; Giorcelli, M.; Ferro, G.A. Improvement in electromagnetic interference
shielding effectiveness of cement composites using carbonaceous nano/micro inerts. Constr. Build. Mater. 2015, 85, 208–216.
[CrossRef]

Electrical Piezoresistive and Electromagnetic Prop

Uploaded by

Copyright:

Available Formats

Electrical Piezoresistive and Electromagnetic Prop

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Electrical Piezoresistive and Electromagnetic Prop

Uploaded by

Copyright:

Available Formats

nanomaterials

College of Civil Engineering, Nanjing Tech University, Nanjing 211800, China;

Nanomaterials 2021, 11, 3220. https://doi.org/10.3390/nano11123220 https://www.mdpi.com/journal/nanomaterials

2.1. Graphene Filler

(c) Reduced Graphene Oxide

Figure 3. Chemical adsorption reaction schematic of GO on cement surface. (a) Adsorption of GO

2.2. Cement Matrix

2.3.1. Dry-Mix Dispersion

(d) Chemical Surface Modification

Unlike TGA and and DTG

Instead of measuring the temperature difference, DSC measures the difference in

Figure 14. XPS

Compared to GO-reinforced CCMs, the –COOH in GO underwent a chemical reaction to

2.4.5. Raman Spectroscopy

GO Content (wt%) Q0 (%) Q1 (%) Q2 (%) Q2 /Q1 MCL α (%)

2.4.7. Mercury Intrusion Porosimetry (MIP)

Wang et al. [26,55,56,84] investigated the porosity and microstructure of GNP/cement

2.4.8. Scanning Electron Microscopy

Nanomaterials 2021, 11, 3220 18 of 32

Table 3. Summary of studies on electrical properties of GRCCMs.

Filler Type Matrix Preparation Electrical Properties Ref.

Nanomaterials 2021, 11, 3220 21 of 32

Figure 25. Experimental

Table 4. Summary of studies on piezoelectrical properties of GRCCMs.

Filler Type Matrix Preparation Piezoelectrical Properties Ref.

The largest strain sensitivity coefficient and stress reached up to

Du et al. [115] studied the piezoresistivity of CCMs incorporated with GNPs by

FigureFigure 27. Piezoresistive

Table 5. Summary of studies on electromagnetic properties of GRCCMs.

Filler Type Matrix Preparation Electromagnetic Properties Ref.

Goracci et al. [114] investigated

Figure 32. (a)

You might also like