Construction and Building Materials 234 (2020) 117403

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Construction and Building Materials

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

Electrochemically produced graphene with ultra large particles enhances

mechanical properties of Portland cement mortar
Van Dac Ho a,b,c, Ching-Tai Ng a, Campbell J. Coghlan b,c, Andy Goodwin d, Craig Mc Guckin d,
Togay Ozbakkaloglu a, Dusan Losic b,c,⇑
a
School of Civil, Environmental and Mining Engineering, The University of Adelaide, South Australia 5005, Australia
b
School of Chemical Engineering, The University of Adelaide, South Australia 5005, Australia
c
ARC Research Hub for Graphene Enabled Industry Transformation, The University of Adelaide, South Australia 5005, Australia
d
First Graphene Ltd, Suite 3, 9 Hampden Road, Nedlands, WA 6009, Australia

h i g h l i g h t s

Pristine graphene (PRG) industrially produced by electrochemical process for cement mortar was explored.

The ultra-large size of PRG particles in average of 56 ± 12 mm was confirmed.

The 0.07% PRG is an optimal PRG dosage with 34.3% and 26.9% enhancement of compressive and tensile strengths at 28 days.

PRG improves the microstructure of the cement matrix.

A strong relationship between mechanical results and bonding gels, densities and arrangements of the crystals is revealed.

PRG is promising a next-generation of additives in cementitious composites.

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

Article history: The effects of the dosages (0.01%, 0.03%, 0.05%, 0.07%, 0.1%, and 0.3% by weight of cement binder) of an
Received 9 July 2019 ultra-large size (56 ± 12 mm) of pristine graphene (PRG) industrialy manufactured by electrochemical
Received in revised form 12 September process on compressive and tensile strengths of cement mortars are presented. To have a better under-
2019
standing of the reinforcement mechanism of PRG-cementitious gels, the physicochemical and
Accepted 26 October 2019
microstructure analyses were performed. The results show that the addition of PRG to cement mortars
improves their mechanical properties, with characteristic concentration dependence. The mortar mix
with 0.07% PRG is identified as the optimal concentration, which provides 34.3% and 26.9% improvement
Keywords:
Pristine graphene
in compressive and tensile strength at 28 days, respectively. This enhancement is attributed to the
Cementitious composites improvement of the hydration degree of cement paste, resulting in more Calcium Silicate Hydrate gel
Compressive strengths production. This also comes from the reinforcement of the adhesion bond that was created from friction
Tensile strengths forces between PRG sheets and cement gels, resulting in strengthening cement matrix composites and
Hydration process impeding crack propagations in the structure. However, with the further increases in PRG contents (i.e.
Microstructures 0.1%, 0.3%), the enhancement of mechanical properties of mortars is limited due to the impact of the
van der Waals force on the sedimentation of PRG suspension, leading to the poor dispersion of the pre-
pared PRG suspension. These results suggests that industrially produced pristine graphene by electro-
chemical process is a promising additive for improving performances of construction materials.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction sive strength. However, they suffer from poor tensile strength, flex-
ural strength, fracture toughness and brittleness giving rise to
Cementitious materials are one of the most commonly used durability issues [1,2]. To overcome these issues, cement materials
materials in the construction industry due to their high compres- are augmented through the use of specific additives, reduction of
water and cement ratios, and reinforcement materials such as
steel, carbon and plastic fibers [3].
⇑ Corresponding author at: School of Chemical Engineering, The University of Recently, cementitious material development has focused on
Adelaide, South Australia 5005, Australia. the incorporation of nanomaterials to not only enhance the
E-mail address: [email protected] (D. Losic).

https://doi.org/10.1016/j.conbuildmat.2019.117403
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

mechanical properties but also retard the propagation of cracks to significantly enhance mechanical properties of cement materials
generate a more durable composite [4]. These studies revealed two [20,22]. For examples, Wang et al. [20] found that the addition of
critical mechanisms [5], which affect the strength of cementitious 0.05% PRG in cement mortar can improve compressive strength
materials in incorporating nanoparticles, such as nano-SiO2 [6], and flexural strength at 7 days, by 8% and 24%, respectively. Tong,
nano-TiO2 [7] and nano-CaCO3 [8], into the cement matrix. The et al. [23] showed that the compressive strength of cement mortar
first is the high specific surface area of nanoparticles, which accel- is improved by 19.9% after 28 days when adding 0.1% PRG by
erates the progression of cement hydration and creates more Cal- weight of cement. However, these earlier studies only focused on
cium Silicate Hydrate (CSH) gels. The second mechanism comes investigating the changes in mechanical properties of cementitious
from the small particle size property, which allows them to act composites between the control mortar and the mix with a certain
as a filler. This grants the material with a denser microstructure. PRG content (e.g. 0.05 or 0.1%) but limited details about properties
However, nanoparticles with low aspect ratios lack competence of used graphene materials [24]. In 2015, Du and Dai Pang [25]
in arresting the propagation of cracks from the nanoscale cracks, studied the properties of cement mortars with four different PRG
they are thus unable to enhance the reinforcement efficiency [9]. dosages (i.e. 0%, 2.5%, 5.0% and 7.5% by weight of cement, with
In addition to inorganic nanomaterials, carbon-based materials, PRG size 8 mm), and showed that the addition of PRG can signifi-
such as nanofibers and nanotubes, have been investigated in cantly decrease water penetration depth. However, their study
cementitious composites as additives and demonstrated they can indicates there are insignificant effects of PRG on compressive
improve the mechanical properties [10,11]. However, these carbon and flexural strengths of cement mortars. This is attributed to
materials showed some limitations to generate a full bonding with the high rate of PRG dosages used, resulting in the agglomeration
cementitious materials due to a lack of interfacial areas between of PRG sheets and forming multi-layers PRG sheets, which results
them [12]. in the hindrance to the interaction between PRG and cement
Graphene, a recently discovered two-dimensional (2D) carbon matrix. A recent study of PRG-cement mortars with different PRG
material, has many outstanding properties such as high electrical concentrations (i.e. 0%, 0.05%, 0.1%, 0.5% and 1% by weight of
and thermal conductivity, high-temperature stability, high cement, with PRG size 5–10 mm) by Tao et al. [26] confirmed that
mechanical strength, ultra-large specific surface areas and high cement mortar with 0.05% PRG additive can improve compressive
aspect ratios. Graphene is widely recognized to be an ideal additive strength and flexural strength at 28 days, by about 8.3% and 15.6%,
to enhance performances of cementitious materials [13,14]. There respectively, but the strengths start decreasing when the PRG
are several different forms of graphene materials such as graphene dosages are increased to exceed 0.05% owing to the agglomeration
oxide (GO), reduced graphene oxide (rGO), pristine graphene of PRG. Although these studies presented the dependence of the
(PRG), doped graphene, and functionalized graphene that have dif- properties of PRG-cement mortars on PRG dosages, the character-
ferent functionality and properties. The pristine graphene pro- istics of the mechanism behind this dependence have not been
duced by a direct exfoliation process from graphite using well understood. Compared to the proposed reinforcement mech-
electrochemical method has different properties compared with anism of GO in cement composites, this is attributed to the strong
rGO, showing less defects, better crystallinity and conductivity. interfacial adhesion between carboxyl, hydroxyl groups and
GO is an oxygenated derivate of graphene prepared by acid oxida- cement matrix [27], which indicates that smaller size GO often
tion of graphite and is water-compatible and highly dispersible. shows a better enhancement rate in mechanical properties of
This is one of the reasons why GO was preferentially explored as cement composites than larger size GO as smaller size GO has more
an additive for improving mechanical performances of cementi- of these functional groups [17,24]. Unlike GO, graphene sheets of
tious composites. Wang, et al. [15] demonstrated that including PRG materials have very few of oxygen groups located at the edges,
0.05% of GO in cement pastes can increase 40.4% and 90.5% in com- where different mechanisms are involved with the friction adhe-
pressive and flexural strength at 28 days, respectively. This was sion forces between PRG sheets and cement matrix. Thus, the lar-
confirmed by Lv, et al. [16]. They reported that GO can enhance ger size of single PRG structure is proposed to have the better
strength and toughness properties of cement composites. Their enhancement to the cement matrix. To date, no studies have been
results show that the compressive strength of cement paste with done to investigate the influence of the ultra-large size of PRG on
0.06% GO is increased by 58.5% after 28 days, while the flexural mechanical properties of cement-based mortars. While graphene
strength is improved by 67.1% after 28 days with the mix having materials are slowly moving into industrial space with many gra-
0.04% GO concentration. Sharma and Kothiyal [17] reported that phene manufacturers around the world that are able to produce
the compressive strength of the cement mortar with 0.1% GO addi- their large quantities, there is still a lack of studies using industri-
tive is increased by 86.3% after 28 days. Recently few studies ally manufactured graphene to improve performances of
revealed the influence of different oxygen functional groups from cementitiou.
GO on the phase composition and intermolecular interaction of To address these research gaps, the aim of this study is to inves-
cementitious materials to help early-age hydration characteristics tigate the use of industrially manufactured PRG produced by an
of the composites [18,19]. Nevertheless, GO material has some lim- electrochemical process with focus on studying the effects of the
itations that could impact its performances in cementitious com- ultra-large size of PRG (i.e. 56 mm) and their dosages (i.e. from 0%
posites. It is less crystalline with a high level of defects and has to 0.3% by weight of cement binder) on the physicochemical and
mechanical properties that are considerably lower than those com- mechanical properties of PRG-cement mortars. Our hypothesis is
pared to PRG or rGO. Therefore, the application of PRG and rGO in that very large sheets of graphene with the size of several tens of
cementitious composites is expected to be more beneficial for micron will significantly improve the mechanical properties of
improving structural performances of cement-based materials cement. Most of the previous studies were based on PRG prepared
[18,19]. in research laboratories with variable quality and less reproducible
Graphene materials, such as rGO and PRG, are highly hydropho- structural and mechanical characteristics. In this work, it is the first
bic and less dispersible in water compared to GO. This is the reason time to use industrially produced PRG manufactured by an electro-
of being less attractive to be incorporated into cement composites chemical process that has recently been established by First
to improve cement performances regardless of their better Graphene Ltd in Perth, Australia, with the capacity of 100 t/year.
mechanical properties [20,21]. Recent studies proved that the To better understand the mechanism behind the positive effects
rGO and PRG dispersion in aqueous solution can be improved by of ultra-large PRG particles with different dosages on cement
a combination of surfactants and ultrasonication method and could mortars, a series of microanalyses were completed using X-ray
 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403 3

diffraction analysis (XRD), Thermogravimetric analysis (TGA), Table 2

Fourier transform infrared spectroscopy (FTIR), Scanning electron Chemical composition of ordinary Portland
cement (OPC).
microscopy (SEM), and Ultraviolet–visible spectrophotometer
(UV–vis). Industrial production of graphene has dramatically Compounds OPC (%)
reduced the cost of producing graphene in large quantities, allow- CaO 63.28
ing it to be incorporated into industrial-scale materials, such as SiO2 19.95
concrete. Hence, the promising results from this study will provide Al2O3 4.79
Fe2O3 3.14
an attractive avenue to practical applications of graphene-based MgO 2.03
materials for a broad range of construction materials to enhance Na2O 0.29
their mechanical and durability properties. K2O 0.4
SO3 2.69
P2O5 0.04
2. Experimental methods

2.1. Materials
of moisture. They continued to be cured in a fog room under the
ambient temperature of 23 ± 2 °C until the testing days (i.e. at
The PRG with the physical properties shown in Table 1 were
7 days and 28 days).
provided by First Graphene Ltd (Australia) from their industrial
The labels of the PRG-cement based mortar mixes shown in
production plant. Ordinary Portland Cement (OPC), which is gen-
Table 5 are designed as follows: the PRG letter is used to refer to
eral purpose cement according to Australian Standard AS 3972-
pristine graphene in the mixes. The number after the PRG letter
2010 [28], with the chemical composition shown in Table 2 were
stands for the proportion of PRG calculated by the weight of Port-
used as the binder of mortar mixes. Natural sand with a 2.36-
land cement in the mixes. To illustrate, PRG0 and PRG0.07 are the
mm maximum particle size was used as the fine aggregate, and
mortar mixes prepared with 0% (i.e. the control mix) and 0.07%
its particle size distribution is presented in Table 3. MasterGlenium
PRG by the weight of cement, respectively.
SKY 8100, which is the second generation polycarboxylic ether
polymer superplasticizer in compliance with Australian Standard
AS 1478.1-2000 [29], was used in all mortar mixes as a surfactant 2.4. Characterization of microstructural tests
to increase the dispersion of PRG in aqueous solution and worka-
bility of mortars. The properties of the superplasticizer are shown 2.4.1. Scanning electron microscopy and particle size measurements
in Table 4. SEM was obtained by using the FEI Quanta 450, which analyzes
and provides high-resolution images of surface topography. The
SEM analysis was conducted at 28 days, and SEM specimens were
2.2. Preparation of PRG suspension
cut from the samples of PRG-cement mortars at 28-day mechanical
tests with the dimensions of about 5  5  5 mm to analyze their
The aqueous solution for mortar mixes, including water, PRG
surface morphologies and microstructures. All these specimens
and superplasticizer, was prepared following the steps: (i)
were dried and then coated by a 5 nm-thick platinum layer to
MasterGlenium SKY 8100 was mixed and stirred in water within
enhance the quality of SEM images. Particle size measurement of
2 min; (ii) PRG was then added and stirred for 2 min; (iii) the solu-
PRG dispersions was measured in triplicate by a Nanosight
tion was then sonicated by Ultrasonicator UIP1000hdT for 30 min
NS300 (Malvern Instruments) coupled with a green laser
to create the aqueous solution for the mortar mixes.
(532 nm) using the O-ring top-plate sample chamber configura-
tion. The pre-installed Nanoparticle Tracking Analysis (NTA) soft-
2.3. Preparation of PRG-cement mortar composites
ware version 3.3 took into account the Brownian motion
trajectory of the particles to measure its size.
A total of seven unique mixes of PRG-cement based mortars
were prepared. Their detailed mix proportions are described in
Table 5. As shown in the table, there are seven concentrations of 2.4.2. X-ray diffraction analysis
PRG used, i.e. 0% (as the plain mortar), 0.01, 0.03, 0.05, 0.07, 0.1 XRD was conducted by using the Rigaku MiniFlex 600 X-Ray
and 0.3% by weight of cement binder. These seven concentrations diffractometer to find the mineralogical characteristics (i.e. the
were designed based on a comprehensive literature review, which crystalline phases) of materials (i.e. OPC, natural sand, PRG, and
focused on investigating the effects of graphene’s derivative (e.g. hydration products of PRG-cement mortars). The XRD was worked
GO, rGO, PRG) on properties of cementitious materials [19,30]. at conditions 40 kV and 15 mA, 2h = 5°–80° at 0.02° step size. The
To prepare the mortar mixes, the procedures described below XRD specimens were collected from remnant pieces of PRG-
were adopted to improve the uniform of the cement matrix: natu- cement mortars at 28-day compression tests, and then, they were
ral sand and OPC were mixed together for four minutes, and then dried in the oven for one day, then ground, and sieved into fine
the aqueous solution (preparation procedures as described in Sec- powders (i.e., < 10 mm) for analysis.
tion 2.2) was gradually added to the mortars and continued mixing
together within five minutes, which contained one minute to check 2.4.3. Thermogravimetric analysis
and stir the mixes. All samples after mounting were vibrated for TGA was performed by using the TGA Q500 instrument to
one minute to eliminate the entrapped air in samples during investigate the effects of PRG on the hydration process of cement
mounting. All specimens were demounted after 24 h cured in room composites at 7 and 28 days. About 20 mg of the powder (i.e.
temperature and covered with wet fabric sheets to prevent the loss < 10 mm) of mortar mixes was heated from room temperature to

Table 1
Physical properties of pristine graphene supplied by First Graphene ltd.

ID Average particle size (mm) Thickness (nm) Purity (%) Bulk density (g/cm3)
PRG-70 56 ± 12 1–3 98.3 0.1
4 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

Table 3
Particle size distribution of natural sand.

Mesh size (mm) 2.36 1.18 0.6 0.15 0.075

Cumulative passing (%) 96.7 84.6 62.2 4.5 0.4

Table 4
Properties of superplasticizer (MasterGlenium SKY 8100).

pH Boiling temperature (°C) Density at 20 °C (kg/dm3) Flash point (°C) Vapour pressure at 20 °C (hPa) Solid content (mass, %)
6.4 100 1.06 >100 23 30.7

Table 5
Mix proportions of the cement mortar composites.

Mix Pristine graphene (%)* Water/cement ratio Cement (kg/m3) Water (kg/m3) Pristine graphene (kg/m3) Sand (kg/m3) Superplasticizer (kg/m3)
PRG0 0 0.485 527 256 0.0 1448 1.4
PRG0.01 0.01 0.485 527 256 0.1 1448 1.4
PRG0.03 0.03 0.485 527 256 0.2 1448 1.4
PRG0.05 0.05 0.485 527 256 0.3 1448 1.4
PRG0.07 0.07 0.485 527 256 0.4 1448 1.4
PRG0.1 0.1 0.485 527 256 0.5 1448 1.4
PRG0.3 0.3 0.485 527 256 1.6 1448 1.4
*
The percentage of pristine graphene based on weight of cement binder.

900 °C with the heating rate of 10 °C per minute under the nitrogen compressive tests. A typical 50 mm cube was used according to the
atmosphere condition. The outcomes of the TGA analysis are able ASTM standard C109/C109M-07 [32]. The direct tensile test with a
to identify the contents of evaporable water (i.e. free water covers dog-bone shaped sample was also conducted at 7 days and 28 days
outer surfaces of cement composites) and non-evaporable water in accordance with the ASTM standard C307-03 [33]. These tests
(i.e. the water content bound by products (e.g. portlandite, calcium were performed to identify the effect of PRG concentrations on
silicate hydrate gels) of the cement hydration process). Based on mechanical properties of PRG-cement based mortars. The com-
the proportion of the weight loss of testing samples, the hydration pressive and tensile strengths were determined from the averaged
degree of cement pastes of the control and PRG-cement samples values of three nominally identical specimens for each mix
was calculated (the details are discussed later in Section 3.4.2). proportion.

2.4.4. Fourier transform infrared spectroscopy

3. Results and discussion
FTIR was performed by using the Nicolet 6700 to determine
specific functional groups and their intensities in samples, includ-
3.1. Characterization of industrial manufactured pristine graphene
ing PRG, cement, sand, powder cementitious materials at 28 days.
(PRG) materials
The infrared spectrum was obtained by using the support of the
spectrum analysis software, which shows spectrums in transmis-
The morphology and physical properties of industrially pro-
sion mode with the range of frequency in wavenumber from
duced PRG material used in this study are summarized in Fig. 1
400 cm1 to 4000 cm1.
and Table 1, which show their morphology, particle size and crys-
tallinity. The graphene particle has irregular shaped structures and
2.4.5. Ultraviolet-visible spectrophotometer the average particle size of the graphene sheets is 56 ± 12 mm and a
UV–vis was obtained by using Shimadzu UV-1601 to investigate carbon content of >98.3%. From Fig. 1(c), the XRD pattern shows
the dispersion of PRG aqueous solution, varying with the time the crystalline phase of PRG at the scattering angle 2h = 26.64°.
between two methods: 30 min sonicated by Ultrasonication UIP The interplanar spacing between layers (i.e. d-spacing) calculated
1000hdT (Hielscher, Germany) and without sonication. The per- based on the Bragg’s Law is 0.334 nm, which is the same as the
centage of the transmittance of PRG aqueous solution determined interplanar spacing of Graphite [24,34], showing a high quality of
by UV–vis varies with time is used to provide a quantitative anal- PRG used in the study.
ysis of the dispersity or sedimentation of the solution. The observations of the sedimentation of PRG in aqueous solu-
tion with times between 30 min sonicated and without sonicated
2.5. Flowability test and mechanical property tests at the same 0.03% PRG content based on the percentage of trans-
mittance of these solutions from UV–vis analysis are shown in
The flow test of fresh mortars was performed immediately after Fig. 2. It is important to note that a solution with a lower percent-
mixed mortars, according to ASTM C1437 [31]. The dimensions of age of the transmittance with time presents for better dispersion of
the truncated cone mold are top diameter 70 mm, height 50 mm, PRG aqueous solution with time. As shown in Fig. 2(a), without a
and bottom diameter 100 mm. The truncated cone mold was filled sonication, the transmittance is high at the early stage about
with fresh mortars by layers and tamped by a tamper to ensure 30%, and continues rising remarkably with time about 70% and
uniform filling of the mold, then the mold was raised vertically, 90% after 4 h and 24 h, respectively. In Fig. 2(b), 30 min sonicated,
and the mean horizontal spreads of fresh mortars were recorded. the transmittance values are low, and rise very slowly with time
This test was conducted to investigate the flowability of PRG- compared to no sonication, which is about 0.5%, 2.5%, and 25% after
cement mortar mixes. For hardened cement composites, the com- sonication, 4 h, and 24 h respectively. From the photos in Fig. 2(c)
pressive strength was determined at 7 and 28 days by carrying out and (d), we can note that the suspension of PRG aqueous solution
 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403 5

Fig. 1. (a) High resolution SEM images showing the size of single PRG particlce and b) Low resolution SEM image (bar scale 50um) and PRG particle size distribution (C) XRD
pattern of PGR material.

Fig. 2. Variation of transmittance of pristine graphene suspension at 0.03% PRG with time from UV–Vis test: (a) without sonication, and (b) 30 min sonication. Photographs of
PRG aqueous suspension after 0 h, 1 h, 2 h, 4 h, and 24 h: (c) without sonication, and (d) 30 min sonication.

without a sonication shows a clear variation of sedimentation fol- 3.2. Effects of PRG on the flowability of PRG-cement mortar composites
lowing the time whereas it is hard to observe the change of the
sedimentation of the one with 30 min sonicated. The results from Fig. 3 presents the flowability of the mortar mixes with differ-
UV–vis and observed photos indicate that the PRG aqueous solu- ent concentrations of PRG. As shown in the figure, the flowability
tion is much more stable and well dispersed with the sonication of the mortars reduces with an increase in the PRG contents, and
method than without sonication, especially within 4 h after the the mean value of the flowability of the control mix is 135 mm,
sonication, which is important to be able to create mixes with high which is 22.7% higher compared to the mix with the addition of
quality because of the effects of initial setting time characteristic of 0.3% PRG (mean value of the flowability is 110 mm). The decrease
OPC on cementitious composites [35]. of the flowability of the mixes with the rise in the PRG contents is
6 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

The trend of the compressive strengths of the mortars at 7 and

28 days decreases when the PRG contents beyond the optimum
value (i.e. 0.07% PRG). The graph in Fig. 4(b) shows that the com-
pressive test results at 7 days of the PRG-cement mortar mixes
with the PRG concentrations under the optimum value have lower
enhancement strength rates than those at 28 days. Whereas, the
trend is upside-down for the mixes with the PRG contents beyond
0.07% PRG.
Fig. 5 describes the 7 and 28 days tensile test results of the dif-
ferent mortar mixes, and their enhancement strengths compared
to the control mix. As shown in the figure, the tensile strength of
the PRG-cement mortars increases with an increase in the PRG
concentrations at all curing ages. It is evident from Fig. 5 that the
optimal concentration of PRG is at 0.07% PRG, which is 3.9 MPa
at 7 days and 4.6 MPa at 28 days, compared to these testing days
of the control mix, which is 3.1 MPa and 3.6 MPa, respectively. This
enhancement in tensile strengths equates to about 25.3% at 7 days
and 26.7% at 28 days. Fig. 5(a) also shows that the tensile strength
of the PRG-cement mortars starts dropping when the PRG contents
beyond 0.07% PRG. From Fig. 5(b), the enhancement strength rates
Fig. 3. Flowability test results of fresh mortars with different PRG contents.
of the tensile test results at 7 days of the PRG-cement mortar mixes
are higher than those at 28 days, except for the mixes PRG0.01 and
attributed to the large specific surface area of PRG, resulting in PRG0.07.
more amount of water required to lubricate their surface sheets, The observed improvement in the compressive and tensile
which is in agreement with the previous research studies on the strengths of the PRG-cement mortar composites with the highest
effects of nanomaterials (e.g. GO, nano-SiO2, PRG) on the flowabil- strength at the PRG0.07 mix, which will be discussed in more
ity of the cement matrix [19,20]. details in Section 3.4, could be explained by the following reasons:
(i) the enhanced cement gels of the cement matrix composite
3.3. Effects of PRG on mechanical properties of PRG-cement mortar owing to: (1) the improvement of the hydration degree of cement
composites pastes due to the high specific surface area of PRG sheets, resulting
in better spreading water to cement particles, which is similar with
The 7 and 28 days compressive test results of the control mix the observation of previous studies on mechanical properties of GO
and the mixes with different PRG concentrations, and their and cementitious composites [9,30]; (2) the closer of cement par-
enhancement strengths compared to the control mortar are shown ticles in the cement matrix caused by the van der Waals forces
in Fig. 4. It can be seen that the addition of PRG to the mortar mixes between PRG sheets, resulting in an enhancement of strengths of
results in an increase in the compressive strength of the cementi- cement gels [30,36]; (ii) the improvement of bonding gels comes
tious composites for both 7 and 28 days compressive test results. from the improved interfacial friction and interconnecting behav-
The optimal concentration of PRG is at 0.07% PRG, which is ior between the crystals of the hydration products in cement gels,
50.0 MPa and 56.3 MPa at 7 and 28 days, respectively. Compared which was created from a part of the covalent bonds between
to these tests with the control mix at the same test days, which some COOH groups in PRG and cement gels (this is similar to other
is 36.5 MPa and 42 MPa, the results show that the strength is studies observed in a combination of carbon nanotube and GO and
enhanced about 36.8% at 7 days and 34.3% at 28 days, respectively. Portland cement [9,37]), and most from friction forces between the

Fig. 4. (a) Compressive strength and (b) enhancement compressive strength of PRG-cement mortars with different proportions of PRG at 7 and 28 days.
 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403 7

Fig. 5. (a) Tensile strength and (b) enhancement tensile strength of PRG-cement mortars with different proportions of PRG at 7 and 28 days.

areas of PRG sheets and cement gels (this was reported in previous this optimal value. It is important to note that the stress-strain
research by using the molecular dynamics simulation method curves can also show the estimated elastic modulus of materials,
[38,39]), resulting in being able to enhance the stress distribution deduced from the ratio between stress and strain which are taken
and impeding the propagation of cracks from nanoscale to micro- at about 40% of the ultimate compressive strength. Therefore, from
scale and macroscale in the cement matrix [19,20]. Nevertheless, Fig. 6, it is concluded that the elastic modulus of the PRG-cement
the mixes with the high PRG concentrations, which are beyond based mortars is higher than the plain mortar, and the mix with
the optimum value, i.e. PRG0.1 and PRG0.3, lead to poor dispersion a higher compressive strength presents a higher elastic modulus.
resulting in the re-stacking of PRG sheets due to the effect of the This trend is consistent with the widespread relationship between
van der Waals force. This is attributed to the creation of multi- compressive strength and elastic modulus in solid materials as
layers PRG sheets with a thicker thickness that results in poor shown in other research or standards [19,41].
interfacial friction and interconnecting behaviour, and thus,
reduces the compressive and tensile strengths. This is in line with 3.4. Microstructure and characterization of PRG-cement mortar
previous findings on GO and cement composites [19,40]. composites
The axial compressive stress and strain relationship of the mor-
tar mixes with different PRG concentrations at 28 days is shown in The influence of the PRG concentrations on the mechanical
Fig. 6. The curves show that for a given PRG concentration, the properties of cement mortar composites at microscale was evalu-
compressive strength increases with an increase in the PRG con- ated using microstructural tests: XRD, TGA, FTIR, and SEM. These
tent, and reaches the highest strength with the PRG0.07 mix, and tests were designed and conducted by four different contents of
then, starts decreasing in strengths when the PRG contents beyond PRG as follows: 0 (the control mix), 0.03% (as shown the transpar-
ently effective effect of PRG), 0.07% (the optimum PRG content
based on the experimental results from mechanical tests), 0.3%
(the maximum PRG content).

3.4.1. XRD analysis

The XRD patterns of OPC, sand, and PRG-cement mortar mixes
are shown in Fig. 7. As shown in Fig. 7(a), the peaks detected in
the XRD pattern for the natural sand are at positions: from 21.2°,
26.7°, 36.7°, to 77.9° etc., which indicates crystalline phases of
quartz in natural sand [42,43]. Fig. 7(a) also shows that the peaks
of diffraction spectra for OPC powder identified the following main
phases: (i) Alite (3CaO.SiO2, C3S) at positions: from 29.5°, 32.3°, etc.
to 62.4°; (ii) Belite (2CaO.SiO2, C2S) at positions: 30.2°, and 32.7°;
(iii) Tricalcium aluminate (3CaO.Al2O3, C3A) at 23.1° and 32.3°;
(iv) Tetracalcium aluminateferrite (4CaO.Al2O3.Fe2O3, C4AF) at
12.3°; and Gypsum (CaO.SO32H2O) at 11.8°. It is also notable from
the figure that C3S shows the major content in the OPC powder, fol-
lowed by C2S, C3A, C4AF, and Gypsum, respectively. These identi-
fied phases and characteristics are in agreement with previous
studies on the OPC components and its hydration process using
the XRD analysis [44,45].
Fig. 6. The axial stress and axial strain relationship of mortar mixes with different In cementitious composites, the main products of the hydrated
PRG contents at 28-day compressive testing. cement paste are portlandite (Ca(OH)2, CH) and calcium silicate
8 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

hydrate (CSH), which contribute to mechanical properties of talline phases of CH in XRD analysis results. In order to make the
cementitious composites, and part of ettringite. The brief hydration equal percentage of natural sand existed in each sample of each
reaction process can be seen in Eqs. (1) and (2) in Section 3.4.2. The mix, the major peak of natural sand at the position 26.7° of each
XRD patterns of the mortar mixes with different PRG concentra- mix was standardized to have equal intensity in all spectra of all
tions, i.e. PRG0, PRG0.03, PRG0.07, PRG0.3, are shown in Fig. 7(b). the mixes [17,46].
Although they have similar types of hydrated productions, their Fig. 7(b), (c) shows that the detected peaks at the scattering
contents are different, resulting in different mechanical strengths angles of 18.2°, 34.2°, and 47.1° correspond with CH phases
(as discussed before in Section 3.3). It is important to note that [44,46]. Fig. 7(c) shows that the intensities of these peaks for port-
CSH gels often stay at the amorphous phases, the XRD analysis is landite in the mixes having PRG (i.e. PRG0.03, PRG0.07, and
thus limited to identify CSH phases [20,45]. However, the content PRG0.3) are higher than the control mix (i.e. PRG0), and are aug-
of CSH gels can be estimated based on the amount of CH (as shown mented with the increase of the PRG contents. It reaches the high-
in Eq. (1) in Section 3.4.2), and the amount of the un-hydrated est value at the PRG0.07 mix, and then decreases when the PRG
cement (e.g. alite) [24,45,46]. The degree of the hydration process concentration beyond 0.07% (i.e. PRG0.3). This suggests that the
of cement mortars can be estimated by the amount of the crys- mixes containing PRG contents have higher degrees of the hydra-

Fig. 7. Powder XRD patterns of: (a) natural sand and original Portland cement; (b) PRG-cement composites with different PRG contents (i.e. 0%, 0.03%, 0.07%, and 0.3%) at
28 days; (c) insets of portlandite and tricalcium silicate details of different PRG-cement composites at 28 days.
 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403 9

Fig. 7 (continued)

tion of cement pastes than the control (as will be also validated by CaCO3 ! CO2 þ H2 O ð5Þ
TGA, FTIR results), which is consistent with the studies on gra-
phene and cementitious composites in literature [20,46]. CaðOHÞ2 þ CO2 ! CaCO3 þ H2 O ð6Þ
Moreover, the major peaks of un-hydrated alite (2h = 29.5°,
Fig. 8(a), (b) shows the TGA analysis results of cement compos-
32.3°) in these mixes detailed in Fig. 7(c) show that the control
ites at 7 and 28 days of curing age, respectively. As shown in Fig. 8
mix has the highest intensity of the amount of un-hydrated alite
(b), from the derivative weight change cures, it can be divided into
than the others, which is followed by PRG0.03, PRG0.3, and
four main loss mass phases: (i) the mass loss below 145 °C is
PRG0.07, respectively. This shows that PRG can accelerate the
referred to as evaporable water and part of bound water [50,51];
degree of the hydration of cement pastes and create more CSH gels
(ii) the mass loss in the range from 145 °C to 200 °C is attributed
in cementitious materials [17,45,46]. In summary, the XRD analysis
to CSH gels (Eq. (3)) [20,48]; (iii) from 350 °C to 500 °C is related
results are in agreement with the growth trend of the mechanical
to the decomposition of portlandite (Eq. (4)) [47,52]; (iv) the mass
strengths of PRG-cement mortar composites discussed previously
loss in the range of 600–700 °C is referred to the composition of
in Section 3.3.
CaCO3 (Eq. (5)) [48,49]. The non-evaporable water and portlandite
contents can be estimated by the following equations [47,48]:
3.4.2. TGA analysis
TGA is another well-known method used to analyze the hydra- Mnonwater ¼ M145 C  M900 C ð%Þ ð7Þ
tion degree of cementitious composites, which is based on the con-
tent of portlandite and non-evaporable water calculated from 74 74
samples [47,48]. According to previous studies on cementitious MCH ¼  MLCH þ  MLCaCO3 ð%Þ ð8Þ
18 44
composites [24,49], the brief chemical reactions of the hydration
performance of OPC and the decomposition reactions of its hydra- where: (i) M145 °C, M900 °C, and Mnon-water present for the mass loss
tion products summarized below can provide a better understand- of sample at 145 °C, 900 °C, and non-evaporable water in percent-
ing to identify different phases in TGA analysis results. age, respectively. (ii) MLCH and MLCaCO3, present for the mass loss
in percentage due to the decomposition of portlandite and CaCO3
ðC3 S; C2 SÞ þ H2 O ! CH þ CSH ð1Þ phases, respectively; MCH stands for the content of portlandite in
percentage, 74 and 74 stand for factors showed the ratios of molecu-
ðC3 A; C4 AFÞ þ GypsumðCaO:SO3 :2H2 OÞ þ H2 O 18 44
lar weight of water in the decomposition phases of portlandite and
n! CaCO3 (as referred to Eqs. (4) to (6)).
! AFt þ AFmðmonosulphoaluminateÞ ð2Þ
r!ðn  rÞ! Based on Eqs. (7) and (8), the amount of portlandite and non-
evaporable water of samples at 7 and 28 days are shown in Fig. 8
ðCSHÞ ! C3 S þ H2 O ð3Þ (a), (b). The contents of portlandite and non-evaporable water
increase with an increase in the curing ages, i.e. 7 and 28 days, in
CaðOHÞ2 ! CaO þ H2 O ð4Þ all the samples, regardless of the PRG concentrations in the mixes,
10 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

Fig. 8. TGA cures show the weight loss as variation of temperature of PRG-cement composites with different PRG contents (i.e. 0%, 0.03%, 0.07%, and 0.3%) at different days:
(a) 7 days; (b) 28 days.

which is in line with other studies on cementitious composites appearance of alkoxy groups (CAO); about from 1300 cm1 to
[19,48]. The PRG mixes show higher percentages of portlandite 1600 cm1 corresponds to aromatic double carbon groups (C@C);
and non-evaporable water than the control at all curing times. In about 1700 cm1 and from 2500 cm1 to 3600 cm1 refers to the
addition, it is evident from the figures that these proportions carboxyl (C@O) and hydroxyl (O–H) groups, respectively. This
increase with an increase in the PRG contents. The highest propor- shows that the existing of carboxylic acid groups (i.e. COOH) in
tion is achieved in the PRG0.07 mix, and then decreased when PRG are in agreement with other studies on graphene composites
using beyond this PRG concentration (i.e. PRG0.3), which is consis- [58,59].
tent with the observed results in the mechanical strengths and Fig. 9(b), (c) shows the FTIR spectra of the plain mix and PRG-
XRD analysis (as discussed before in Sections 3.3 and 3.4.1). In cement mixes at 28 days of curing age. The group bands in the
summary, from the TGA analysis results, the PRG can accelerate ranges of 400–550 cm1 and 800–1200 cm1 represent for SiAO
the hydration degree of cementitious composites, which is in bonds in the CSH gels [55,60]. A broad band from 2800 to
agreement with the previous finding in graphene and cement 3600 cm1 attributed to O–H groups in water molecules belongs
matrix composites [19,20,47]. to CSH gels in the mixes [55,56,60]. The narrow vibration in the
range of about 3500–3600 cm1 corresponds to OAH bonds in
3.4.3. FTIR analysis CH (portlandite) [55], and CAO bonds in (CO3)2 groups observed
The FTIR spectra of natural sand, OPC, and PRG are shown in in a range of 1350–1550 cm1 [56,60]. From Fig. 9(b), (c), it is evi-
Fig. 9(a). The major bands observed for natural sand are: the asym- dent that the intensities of spectra represented for CSH gels (i.e.
metrical bending vibration of SiAOASi at about 470 cm1; the SiAO, HAOAH), CH (i.e. OAH), and CaCO3 (i.e. (CO3)2) in PRG-
band at about 520 cm1 attributed to the asymmetrical bending cement mixes (i.e. PRG0.03, PRG0.07, PRG0.3) are stronger than
vibration of SiAOAAl; the symmetrical bending variation of SiAO those of the control mix (PRG0). This is attributed to higher hydra-
observed at about 692 cm1 presents the crystalline form of quartz tion degrees in PRG-cement pastes, which results in the enhance-
in natural sand; the band from 750 to 810 cm1 is attributed to the ment of mechanical properties of the PRG mixes. This is
symmetrical stretching variation of SiAO; and the asymmetrical consistent with mechanical properties, XRD, TGA results discussed
stretching variation from about 950 to 1100 cm1 for SiAO. All before, and in agreement with previous studies on graphene in
observed bands for natural sand from FTIR analysis results are in cementitious composites [56,58,60]. Moreover, at a given PRG con-
agreement with previous studies on natural sand using infrared centration, the intensity of the spectrum of PRG0.07 shows the
spectrum [53,54]. strongest band, followed by PRG0.3 and PRG0.03 respectively. This
For OPC, the bands at about 450 cm1 and 525 cm1correspond is consistent with the trend curves of the mortar mixes in compres-
to out-of-plane and in-plane bending vibrations of SiAO bonds and sive and tensile strengths as discussed earlier in Section 3.3.
stretching vibration from about 800 cm1 to 1000 cm-1with peaks
at about 879 and 935 cm1 correspond to SiAO bonds within the 3.5. SEM cross-sectional analysis
SiO4 groups. These bands are attributed to C3S and C2S main con-
stituents in OPC [55–57]; the AlAO bending vibration at about The SEM images of cracking patterns of the mortar mixes, i.e.
720 cm1 is belong to AlO4 groups in C3A composition in OPC PRG0, PRG0.03, PRG0.07, and PRG0.3, at 28 days at 50 mm and
[55,56]; two bending vibrations at about 600 and 650 cm1 and 30 mm magnification are shown in Fig. 10. The density and width
the stretching band from about 1050 to 1150 cm1 correspond to of micro-cracks lead to a reduction in bonding, interconnecting,
the SAO bonds within SO4 tetrahedral groups, belong to the gyp- and interfacial friction properties of cementitious composites as
sum constituent in OPC [56,57]; the stretching variation from shown in these SEM images. The control mix (Fig. 10(a), (b)) shows
1370 cm1 to 1520 cm1 is attributed to (CO3)2- in OPC [57]. a higher degree of cracks both in the density and size and the lower
The major bands of PRG showed the stretching vibrations: from compactness of the microstructure than those in PRG0.03,
about 1000 cm1 to about 1240 cm1, which represents the PRG0.07, and PRG0.3, as shown in Fig. 10(c)–(h), resulting in the
 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403 11

Fig. 9. FTIR spectra of: (a) PRG, OPC and NS; (b, c) PRG-cement composite mixes with different PRG contents (i.e. 0%, 0.03%, 0.07%, and 0.3%) and their insets at 28 days.

lower strengths of the control mix than the others. Thus, the PRG- between crystals [16,17,24]. It can be observed that they have sim-
cement based mortars with better microstructures have the effi- ilar types of the compositions in microstructures while the density
cient capacity in crack bridging, crack branching and stress distri- and distribution of these components in each sample are different.
bution, and also impeding crack propagations in structures, which For PRG0 shown in Fig. 11(a), (b), it not only shows fewer contents
leads to significant enhancement of compressive and tensile and smaller sizes of CSH and CH crystals, but also consists of signif-
strengths. This is consistent with the results discussed in previous icant numbers of pores in its microstructure. This leads to smaller
sections and also in agreement with the observations of other stud- mechanical strengths than those of the PRG-cement mixes (as con-
ies on graphene and cement materials [17,19,20,47]. sistent with the results discussed in the previous sections).
Fig. 11 shows the high magnification at 10 mm and 5 mm of SEM By the addition of the 0.03%, 0.07%, and 0.3% PRG content
images of the mortar mixes with different PRG concentrations, i.e. (Fig. 11(c)–(h)), there are apparent changes in their microstruc-
0%, 0.03%, 0.07%, and 0.3%, at 28-day curing age. The SEM images tures with larger sizes and enhanced densities of crystals, also
show four main compositions of the microstructures of the sam- more compactness. The best observation in the change of the
ples: CSH gels have tetrahedral and polyhedral shapes; CH has microstructure can be seen in PRG0.07 (Fig. 11(e), (f)), which is
hexagonal shapes; Aft has needle-rod shapes; and pores intercalate the densest, and followed by PRG0.3 (Fig. 11(g), (h)) and PRG0.03
12 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

Fig. 10. SEM images of cracking patterns at 50 mm and 30 mm magnification of PRG-cement mortar mixes with different PRG contents (i.e. 0%, 0.03%, 0.07%, and 0.3%) at
28 days: (a, b) PRG0; (c, d) PRG0.03; (e, f) PRG0.07; (g, h) PRG0.3.

(Fig. 11(c), (d)). This is because PRG0.07 not only shows the highest XRD, TGA, and FTIR results, but also comes from the mechanical
degree of the cement hydration, which was discussed earlier in adhesive friction forces between PRG sheets and cement gels,
 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403 13

Fig. 11. High magnification at 10 mm and 5 mm of SEM images of PRG-cement mortar mixes with different PRG contents (i.e. 0%, 0.03%, 0.07%, and 0.3%) at 28 days: (a, b)
PRG0; (c, d) PRG0.03; (e, f) PRG0.07; (g, h) PRG0.3.

resulting in the strong interconnection across the compositions of (2) It has been shown that the addition of PRG to cement mor-
cement matrix composites. tars can improve their mechanical properties and the level of
When PRG concentration is increased up to 0.3%, it leads to poor improvement depends on PRG contents. The 0.07% PRG mix
dispersion. The agglomeration of PRG sheets occurs due to the has been identified as the optimal PRG concentration in this
effect of the van der Waals force. This creates multi-layers PRG study, which provides 34.3% and 26.9% enhancement of
sheets with thicker thickness, and hence, it prevents PRG sheets compressive and tensile strengths at 28 days, respectively.
to contribute to improve the degree of the cement hydration pro- (3) PRG has improved the microstructure of the cement matrix,
cess and to interact with the crystals compositions of cement gels. which comes from the rise in the hydration degree of
This leads to the reduction in mechanical strengths, which is in line cement pastes and the adhesive friction forces between
with the results discussed in the previous sections and previous PRG sheets and cement gels, and has also impeded crack
studies on a combination of graphene and cementitious compos- propagations in the structures.
ites [19]. (4) The mixes with the PRG contents, which are higher of the
optimal value (i.e. 0.07%), lead to poor dispersion resulting
4. Conclusions in the agglomeration of PRG sheets. This limits the improve-
ment of the mechanical strengths.
The results of the investigation on the effects of different con- (5) The results from XRD, TGA, FTIR, and SEM analyses have
centrations of industrially produced PRG by electrochemical exfo- shown that there is a strong relationship between mechani-
liation of graphite on the physicochemical and mechanical cal results and bonding gels, densities and arrangements of
properties of PRG-cement mortar composites have been presented. the crystals in the microstructures.
The following key conclusions have been drawn based on the
results and discussions in the study: The results and findings from this study have suggested a
promising capability of industrially manufactured PRG using elec-
(1) The first study of the ultra-large size of PRG particles in aver- trochemical process due to their unique properties to be used as a
age of 56 ± 12 mm produced by this industrial process has next-generation of additives in cementitious composites. This
been confirmed that there is a significant enhancement of could improve the properties of building materials, such as
the ultra-large PRG size to mechanical properties of cemen- mechanical, durability, conductivity, and shielding properties. We
titious composites, compared to all previous studies using are currently in the process of investigating the effects of the dif-
graphene based materials. ferent contents, sizes and types of PRG on these properties, and
the findings will be presented in separate studies.
14 V.D. Ho et al. / Construction and Building Materials 234 (2020) 117403

Fig. 11 (continued)

Declaration of Competing Interest [5] F. Sanchez, K. Sobolev, Nanotechnology in concrete–a review, Constr. Build.
Mater. 24 (11) (2010) 2060–2071.
[6] T. Ji, Preliminary study on the water permeability and microstructure of
The authors declare that they have no known competing finan- concrete incorporating nano-SiO 2, Cem. Concr. Res. 35 (10) (2005) 1943–
cial interests or personal relationships that could have appeared 1947.
[7] L. Senff, D. Tobaldi, S. Lucas, D. Hotza, V. Ferreira, J. Labrincha, Formulation of
to influence the work reported in this paper.
mortars with nano-SiO 2 and nano-TiO 2 for degradation of pollutants in
buildings, Compos. B Eng. 44 (1) (2013) 40–47.
Acknowledgements [8] W. Li, Z. Huang, T. Zu, C. Shi, W.H. Duan, S.P. Shah, Influence of nanolimestone
on the hydration, mechanical strength, and autogenous shrinkage of ultrahigh-
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This work is supported and funded by the ARC Research Hub for [9] Z. Pan, L. He, L. Qiu, A.H. Korayem, G. Li, J.W. Zhu, F. Collins, D. Li, W.H. Duan, M.
Graphene Enabled Industry Transformation (Grant IH150100003) C. Wang, Mechanical properties and microstructure of a graphene oxide–
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