Construction and Building Materials 270 (2021) 121462

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Construction and Building Materials

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

The synergic effects of metakaolin and polycarboxylate-ether on

dispersion of graphene oxide in cementitious environments and macro-
level properties of graphene oxide modified cement composites
Kasra Amini, Ali Ghasemi, Siavash Soleimani Amiri, Sajjad Mirvalad ⇑, Asghar Habibnejad Korayem
School of Civil Engineering, Iran University of Science and Technology, Tehran, Iran

h i g h l i g h t s

The potential of MK and MK-PCE against GO aggregation was comparatively evaluated.

MK alone was not capable of preventing the GO aggregation in cementitious solution.

The incorporation of MK-PCE significantly improved the stability of GO in SCPS.

The optimal range of the ultrasonication energy for MK-PCE-GO sample was 25–40 KJ.

The effect of MK-GO was more than the pure GO in enhancing the mechanical properties.

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

Article history: Studying the effects of pozzolanic materials such as silica fume, fly ash, and metakaolin (MK) on disper-
Received 17 August 2020 sion of graphene oxide (GO) in cementitious environments has attracted interest in recent years. In this
Received in revised form 7 October 2020 research, the potential of MK particles as an impediment against GO agglomeration in high alkaline envi-
Accepted 14 October 2020
ronments is investigated. Despite the exhibited results in previous studies that the particles of pozzolans
Available online 12 November 2020
can inhibit the agglomeration of GO in cementitious environments by consuming Ca(OH)2 besides the
mechanical separation of GO sheets, the results of the present study revealed that MK particles alone
Keywords:
could not prevent GO nanosheets from clustering, physically or chemically. However, based on UV–vis
Graphene oxide
Metakaolin
spectroscopy and SEM-EDS analysis results, the incorporation of MK particles with Polycarboxylate-
Polycarboxylate-ether ether (PCE) significantly ameliorates the dispersion and time-dependent stability of GO nanosheets in
Simulated cement pore solution simulated cement pore solution. Indeed, in this case, the anchoring characteristic of the negative surface
Dispersion charge of MK particles besides the steric hindrance effect of PCE’s side chains can reduce the possibility of
Cement composites the interaction between GO nanosheets and calcium ions in cementitious environments. Moreover, the
Mechanical properties improved stability of MK-PCE modified GO suspensions ensures the permanence of the desired dispersion
of GO in the alkaline medium of cement composites, which is advantageous for enhancing the mechanical
and transport properties of cement composites. In this research, the results of compressive strength, flex-
ural strength, flexural modulus, toughness, and ultrasonic pulse velocity tests on MK-GO incorporated
cement paste samples after 28 days of curing showed an enhancement by 27.6%, 36.3%, 49.8%, 42.0%,
and 5.0%, respectively compared to the reference sample. This improvement is primarily due to the ben-
eficial effects of MK-PCE to make GO play a better reinforcing role in cement composites.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction of the properties of cement composites that leads to the construc-

Over the past decade, the use of nanomaterials as a new gener-
ation of cement additives has attracted a growing interest in
cement-based materials. This desire arises from the amelioration
⇑ Corresponding author.
E-mail address: mirvalad@iust.ac.ir (S. Mirvalad).
tion of stronger, more durable, and more versatile structures [1–3].
Graphene is a two-dimensional nanomaterial with extraordinary
properties such as an outstanding elastic modulus of ~1000 GPa,
a large specific surface area of 2630 m2/g, and high thermal con-
ductivity (5300 W m1 K1) [1,4–6]. GO is a derivative of graphene
which contains oxygen functional groups like hydroxyl, epoxide,
carboxyl, and carbonyl. The Young’s modulus of a monolayer of
GO is about 207.6 ± 23.4 GPa and its specific surface area is

https://doi.org/10.1016/j.conbuildmat.2020.121462
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
approximately in the range of 1657–1807 m2/g [7,8]. The presence
of the polar functional groups on the GO’s basal plane ensures its
good dispersion in aqueous solutions and increases its ease of
use [9,10].
Previous studies revealed that the Ca2+ cations and OH anions
in the cement pore solution are an important barrier against the
suitable dispersion of GO since they can agglomerate GO
nanosheets [11,12]. Henceforth, to make optimal usage of GO
nanosheets in cement composites, it is necessary that the good dis-
persion of GO nanosheets in the alkaline cementitious environ-
ment be guaranteed since the agglomeration of GO by Ca2+
cations could reduce the reinforcing properties of GO nanosheets
[13–16]. For instance, these agglomerates may cause stress con-
centration in cement composites [17,18]. With this in mind, some
methods such as mechanical ultrasonication, chemical functional-
ization, and the usage of surfactants have been suggested by previ-
ous studies to improve the dispersion and stability of GO
nanosheets in cementitious environments [9,12,19,20]. Although
a mild ultrasonication is enough to reach the good dispersion of
GO nanosheets in aqueous solutions, it is necessary to take the
advantages of using other aforementioned methods in cementi-
tious environments. Employing the surfactant treatment is one of
the most effective and also easiest ways that can prevent the clus-
tering of GO nanosheets. The appropriate surfactant should be cho-
sen carefully as different effects are reported for them [12,21–25].
In the past works [12,25], various surfactants and water-reducing
agents such as naphthalene based superplasticizer (NSF), sodium
dodecyl sulfate (SDS), lignosulfonate (LS) and polycarboxylate
(PC) based superplasticizers have been used to modify the disper-
sion of GO nanosheets in high alkaline environments.
By and large, recent studies have demonstrated that polycar-
boxylate (PC) based superplasticizers not only improve the fluidity
of cement composites but the GO dispersion in cementitious envi-
ronments [9,12,22–25]. The results show that PCE macro-
molecules have performed much better in promoting the disper-
sion of GO nanosheets compared with other surfactants and
copolymers [12,25]. PC copolymer with a comb-like structure com-
posed of a non-polar backbone with carboxylate (COO) anchor
anions on its surface as well as side chains with low polarity. The
__
COOH groups on the surface of GO and __COO units on the
PC’s backbone form a covalent bond and consequently GO plane
would be coated by PC [24]. In addition, PC reduces the concentra-
tion of free Ca2+ in the cement pore solution by the interaction
between carboxylate anchors and calcium cations; moreover, PC
can hamper the agglomeration of GO sheets through steric hin-
drance caused by its side chains that take adjacent ions away from
the surface of GO [25]. The results of using the mix of GO and PC
(GO 0.022% and PC 0.220% by mass of cement) in cement mortars
after 28 days of curing showed a 22.59% increase in compressive
strength and 24.56% increase in flexural strength in comparison
with the reference sample. On the contrary, by overusing PC, the
bleeding effect that has an adverse influence on the strength of
cement composites would be probable [26].
Pozzolans are another kind of cement additives that have the
ability to be used in the construction industry due to their low cost,
easy accessibility, and also environmental considerations. By sub-
stituting a part of cement with these materials, cement consump-
tion and subsequently CO2 emission could be reduced as the
cement industry produces significant amounts of carbon dioxide.
Pozzolanic materials such as silica fume, metakaolin, fly ash, rice
husk ash, and blast furnace slag react with Ca(OH)2 as a cement
hydration product and produce the secondary C-S-H gel that could
contribute to the enhancement of the mechanical and durability
properties of cement composites [27–30]. Metakaolin with a
non-crystalline structure is produced by calcination of kaolinite
clay between 500 °C and 800 °C [31,32]. Recently, besides using
2
Construction and Building Materials 270 (2021) 121462
surfactants such as PCE in order to promote the dispersion of GO
nanosheets, some studies have investigated using silica fume par-
ticles as a pozzolanic material to mechanically separate GO
nanosheets in cementitious environments and also to reduce the
concentration of Ca2+ in the cement pore solution through the poz-
zolanic reaction [11,22,33]. Therefore, to shed light on the method
of using pozzolans to disperse GO nanosheets in cementitious
environments, it is necessary to investigate the influence of other
pozzolans with different compositions and structures.
The aim of the present study is to comparatively evaluate the
dispersion and stability status of GO in high-alkaline environments
through the incorporation of MK and MK-PCE. With this intention,
firstly, the dispersion of MK modified GO suspensions in the simu-
lated cement pore solution (SCPS) was investigated to reveal the
ability of MK particles alone to prevent GO agglomeration. Then,
the influence of MK-PCE, compared to the PCE alone, on dispersion
and stability of GO in SCPS was examined by a series of experi-
ments including UV–vis spectroscopy, zeta potential measure-
ment, dynamic light scattering (DLS) test, laser diffraction
particle size analysis and also scanning electron microscopy
(SEM) characterization. Eventually, the outcomes of dispersion
experiments were assessed by performing the mechanical strength
tests and also ultrasonic pulse velocity (UPV) measurements on the
cement paste and mortar specimens.
2. Materials and methods
2.1. Raw materials
2.1.1. Cement, metakaolin, and sand
Ordinary Portland cement produced by Tehran Cement Plant
(Iran), conforming to the requirements of Type II, as mentioned
by ASTM C150/C150M-16 [34] was used for preparing cement
paste and mortar specimens. Also, metakaolin was supplied by a
local producer. In this study, standard sand in accordance with
ASTM C778-13 [35] criteria was employed to fabricate cement
mortar specimens. The gradation of sand is listed in Table 1. Also,
the chemical composition and physical properties of cement and
metakaolin are shown in Table 2. For more identification, the par-
ticle size analysis was conducted on cement and metakaolin in the
solid-state using the laser diffraction technique, and the resulted
particle size distribution graphs are shown in Fig. 1(a). Addition-
ally, X-ray diffraction (XRD) test was performed on cement and
metakaolin to determine the mineralogical phases existing in their
chemical structure. The XRD patterns of cement and metakaolin
besides their main constitutive phases are presented in Fig. 1(b)
and (c), respectively. Moreover, it is worth mentioning that unlike
the XRD pattern of cement, fewer peaks are seen in the metakaolin
XRD pattern due to the amorphous structure of this material.
2.1.2. GO
GO suspensions with two different concentrations of 1 mg/ml
and 4 mg/ml were purchased from NAMAGO Company. The first
one was used in dispersion characterizations while the latter one
Table 1
Gradation of standard sand.
Sieve size (mm) Passing sieve (%)
ASTM C778-13 Experimental program
1.18 100 100
0.600 96–100 98
0.425 65–75 65
0.300 20–30 23
0.150 0–4 4
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Table 2
Chemical composition and physical properties of Portland cement and metakaolin.

Material Chemical composition (%) Bogue composition (%) Physical properties

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O LOI C3S C2S C3A C4AF Specific gravity Blaine (cm2/g)
Cement 19.42 3.63 3.23 63.01 2.69 6.79 – 0.71 1.70 60.55 10.07 4.15 9.81 3.12 3472
Metakaolin 74.23 15.33 1.01 5.05 0.18 0.27 – 0.62 2.92 – – – – 2.40 3818

Fig. 1. (a) Particle size distribution of cement and metakaolin; XRD pattern of (b) cement and (c) metakaolin.

was employed for casting cement paste and mortar samples. The
elemental analysis of as-received GO suspensions provided by
the manufacturer is listed in Table 3. Moreover, the transmission
electron microscopy (TEM) image of as-received GO sheets is pre-
sented in Fig. 2(a). As can be seen, the most noticeable observation
is the wrinkled morphology of GO sheets due to the intercalation of
plentiful oxygen-containing functional groups on their surfaces.
Also, the lateral size of as-received GO sheets was approximately
in the range of 3–6 lm based on the TEM characterization. To
investigate the degree of dispersion of as-received GO suspension
in deionized water, UV–vis spectroscopy according to the Beer-
Table 3
Elemental analysis of GO.
Element Carbon Nitrogen Sulfur
Percentage (%) 58–63 0–2 1–2
Lambert law (Abs ¼ ecl; Eq:ð1Þ) was conducted on a diluted sample
of the as-received GO suspension. Fig. 2(b) shows the UV–vis spec-
trum of diluted GO suspension. Two specific peaks are obvious in
this spectrum, first situated at 230 nm that is attributed to the
p-p* electron transitions of C=C bonds. Another peak at 300 nm
in the form of a shoulder corresponds to the n-p* electron transi-
tions of C=O bonds. The AFM image of GO nanosheets was charac-
terized using an Atomic force microscope (ENTEGRA AFM, NT-
MDT). First, GO suspension was subjected to a mild ultrasonication
using an ultrasonic bath sonicator and then a droplet of it was
deposited on a clean mica surface for AFM imaging that is shown
in Fig. 2(c). Fig. 2(d) illustrates that the average thickness of GO
nanosheets was approximately 1.34 nm which could be a result
of the exfoliation of GO into a monolayer as reported in the litera-
Oxygen ture [36,37]. Moreover, as can be seen from Fig. 2(e), the lateral
dimension of GO sheets was less than 1 lm which mainly could
33–38
be due to the effects of ultrasonication treatment.
3
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Fig. 2. (a) TEM image of as-received GO nanosheets. (b) UV–vis spectrum of GO in water and AFM image of GO with a concentration of 0.01 mg/ml dried on the mica surface,
(c) top view (d) height profile for the blue section specified in the picture and (e) three-dimensional view of GO sheet. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)

2.1.3. Superplasticizer
A polycarboxylate ether-based (PCE) superplasticizer conform-
Table 4
ing to ASTM C494/C494M-16 [38] Type F requirements was uti-
Properties of polycarboxylate ether-based superplasticizer used in this study.
lized for dispersion experiments and also to achieve the desired
workability of cement paste and mortar mixtures. The properties Appearance Slightly yellow liquid
of the superplasticizer are represented in Table 4. Also, for obtain- Specific gravity (g/cm3) 1.03
ing more information about the chemical structure of the used Solid content 50%
pH ~7
superplasticizer, nuclear magnetic resonance (1HNMR) analysis
Recommended dosage by manufacturer 0.2–0.8% by mass of cement
was conducted on a droplet of PCE using a 500 ultrashield spec-
4
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Fig. 3. HNMR spectrum of PCE.

trometer (Bruker). It should be noted that the D2O solvent was
employed for dissolving PCE before 1HNMR characterization. The 1-
HNMR spectrum of PCE is shown in Fig. 3. The peak at 2.28 ppm
indicated the existence of -CH in the main chain of PCE macro-
molecules. Also, the peak at 3.26 ppm was due to the presence of
-CH3 in PCE. The major peak at 3.59 ppm was related to -CH2-
CH2-O- (PEO) in the side chain of PCE macro-molecules. Moreover,
the presence of the D2O solvent was responsible for the strong
peak at 4.70 ppm.
2.2. Preparation of simulated cement pore solution (SCPS)
Moreover, it should be pointed out that the mixes containing indi-
vidual GO and also PCE modified GO were prepared as the refer-
ence mixes for some dispersion characterizations. The mass
ratios of PCE/GO were chosen among the most employed ratios
in the literature [12]. On the other hand, the volume of the suspen-
sions was set so that the various requirements of the characteriza-
tions would be satisfied. Prior to each characterization, the
prepared suspension was subjected to sonication for 10 min set
as 50 W using a cup-horn sonicate processor for its homogenizing.
The mix proportions of the prepared suspensions for dispersion
characterizations in SCPS are tabulated in Table 7.

SCPS was prepared based on the suggested recipe by Ghods 2.4. Fabrication of cement paste and mortar specimens
et al. [39] as displayed in Table 5. In order to prepare the SCPS,
the NaOH and KOH pellets in addition to powdered Ca(OH)2 and Four mixtures were fabricated for cement paste and mortar
CaSO42H2O (all produced by Merck company) were poured into samples. The first one which was considered as the reference (con-
deionized water (pH = 6.7). It should be indicated that the solution
was saturated with Ca(OH)2. In the next step, the solution was
mixed with a magnetic stirrer at 1000 rpm for 5 min. After that, Table 6
to produce a transparent solution without any solid particles, the The concentration of different elements in SCPS determined by ICP-OES.
solution was filtered with a filter paper twice. The elemental com- Element concentration
position of SCPS was analyzed by inductively coupled plasma- (ppm)
optical spectrometry (ICP-OES, Varian 730-ES). The results are pre- Ca Fe Na K Si
sented in Table 6. The pH of the prepared SCPS for dispersion char-
780.05 0.01 3943.4 7518.8 1.6
acterizations was approximately in the range of 13.3–13.5.

2.3. Mix proportions of dispersion characterizations

Based on the previously most used proportions of MK and GO Table 7

Mix proportions of GO and MK-GO suspensions in SCPS.
by mass of cement, four different mass ratios of MK/GO including
100, 300, 600, and 1000 were selected for performing dispersion Mix number Dispersant suspension Matrix type PCE:GO
characterizations on MK-GO and MK-PCE-GO suspensions in SCPS. (mg) volume (mL) (mass ratio)a
MK GOb
1 – 2 50 SCPS 0, 2, 5, 20, 40
Table 5
2 200 2 50 SCPS 0, 2, 5, 20, 40
The amounts of chemicals required for fabrication of SCPS.
3 600 2 50 SCPS 0, 2, 5, 20, 40
Added compound (g/l) 4 1200 2 50 SCPS 0, 2, 5, 20, 40
5 2000 2 50 SCPS 0, 2, 5, 20, 40
Ca(OH)2 NaOH KOH CaSO42H2O
a
The mass ratio is based on the concentration of both PCE and GO.
Saturated 8.00 22.44 27.55 b
The ultimate concentration of GO was set to 0.04 mg/ml.

5
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
trol) mix was composed of ordinary Portland cement (OPC) and
water; while the second one was prepared with 9% of cement
replacement by MK. The third one was prepared through the incor-
poration of diluted GO solution into the OPC at the dosage of 0.03%
by mass of the cement. On the other hand, GO and MK were incor-
porated into the fourth mix at 0.03% and 9% by mass of the binder
(a combination of OPC and MK), respectively. The water to binder
ratio (w/b) was set to 0.4 for all of the cement paste mixes, while
the ratio of water to binder was kept constant at 0.485 for the
cement mortar mixes. Moreover, the mass ratio of binder to stan-
dard sand was 1:2.75. Based on the outcomes of the dispersion
experiments of MK-PCE modified GO and to attain the desired
workability, PCE was added to cement paste and mortar mixtures
at the dosages of 0.2% and 0.4% by mass of the binder, respectively.
Mixing procedures were based on the ASTM C305-14 [40] instruc-
tion for both of the cement paste and mortar mixtures. However, it
is worth mentioning that to make cement paste and mortar spec-
imens containing the MK-GO hybrid, firstly, MK and PCE were
added to the diluted GO solution for pre-dispersing GO nanosheets
prior to mixing with cement. After the completion of the mixing,
the cement paste and mortar mixtures were cast into the molds.
Each mold was vibrated using a vibration table to ensure good
compaction. Also to hinder moisture loss of the cement paste
and mortar samples, the molds were covered by a thin plastic
layer. The specimens were demolded after 24 h and cured in
water-saturated by calcium hydroxide at 20 ± 2 °C up to the testing
time.
2.5. Experiments
2.5.1. UV–vis spectroscopy
For investigating the dispersion state of the pure GO and MK
modified GO suspensions besides their PCE incorporated suspen-
sions in SCPS, UV–vis absorption spectroscopy was conducted
using a double beam spectrophotometer (PG Instruments, T80+)
in the wavelength range of 200–700 nm. For the purpose of sepa-
rating solid particles of the suspensions, all of the samples were
centrifuged at the speed of 12,000 rpm for 6 min before testing.
The ultimate concentration of GO was maintained at 0.04 mg/ml
in all of the samples. The volume of 3 ml of samples were poured
into a quartz cuvette and the test was conducted.
2.5.2. Zeta potential
To evaluate the interaction between GO nanosheets and MK-
PCE hybrid in SCPS, zeta potential analysis was performed by
means of a zeta potential analyzer (Horiba Jobin Yvon, SZ-100z).
It should be indicated that the KOH solution was employed for
adjusting the pH of the suspensions in SCPS which had high alka-
linity. For the sake of reliability, measurements were repeated
three times and the mean values were reported.
2.5.3. Particle size distribution analysis
The particle size distribution of the pure GO and MK modified
GO suspensions besides their PCE incorporated suspensions in
SCPS was investigated by dynamic light scattering (DLS) and laser
diffraction (LD) techniques to further assess the influence of MK
and PCE on dispersion of GO nanosheets in SCPS. Based on the pre-
arranged visual observations, the particle size distribution of PCE-
GO in SCPS was obtained using the DLS technique (Horiba Jobin
Yvon, SZ-100z); while the particle size distribution of the other
suspensions in SCPS was analyzed by LD technique (Sympatec
Helos, H2396).
2.5.4. SEM characterization
SEM micrographs were taken by a field emission scanning
electron microscope (JEOL, 7001F FEG). A droplet of the suspension
6
Construction and Building Materials 270 (2021) 121462
was dropped on a silicon substrate and after drying, the
sample made conductive by coating a thin layer of platinum. In
addition, energy-dispersive X-ray spectroscopy (EDS, Oxford
Instruments, AZtec) was served as an elemental analyzer of the
samples.
2.5.5. Mechanical properties of cement paste and mortar samples
Compressive and flexural strength tests were carried out using a
universal testing machine (SANTA, STB-504) with a capacity of 50
kN. Moreover, it should be pointed out that both of the compres-
sive and flexural strength tests were conducted at the curing ages
of 3, 7, 28, and 90 days on the cement composite samples. In the
case of cement paste samples, the compressive strength tests were
performed on 15 mm  15 mm  15 mm cubic specimens accord-
ing to the ASTM C109/C109M-16a [41] procedure; while the flexu-
ral strength tests were conducted on 15 mm  15 mm  80 mm
prismatic specimens following the ASTM C78/C78M-16 [42] proce-
dure. Furthermore, the loading rate was set to 0.2 mm/min for both
of the compressive and flexural strength tests. On the other hand,
in the case of cement mortar samples, the prismatic specimens
with dimensions of 40 mm  40 mm  160 mm were subjected
to three-point flexural testing in accordance with ASTM C348-14
[43] procedure. The loading rate on the flexural samples was
0.2 mm/min. Also, the compressive strength tests were conducted
on residual flexural broken samples, according to the ASTM C349-
14 [44] procedure with a loading rate of 1800 N/s. It is worth men-
tioning that for the reliability of the test results, four specimens of
each mixture were tested at all ages and the mean values of the
recorded results were reported as the compressive and flexural
strength.
2.5.6. Ultrasonic pulse velocity measurement
An ultrasonic pulse meter (Proceq, Pundit Lab+) was utilized to
measure pulse velocities through the cubic cement paste
(15 mm  15 mm  15 mm) and prismatic cement mortar
(40 mm  40 mm  160 mm) specimens in accordance with ASTM
C597-16 [45] criteria. Prior to testing the specimens, the instru-
ment was calibrated by a calibration rod to ensure its accuracy.
Also, both single pairs of transducers were lubricated to facilitate
pulse transmission to both faces of the specimen. Each round of
testing was repeated 3 times for 4 specimens of each mix and
the mean values were reported.
3. Results and discussions
3.1. Investigation of the dispersion and stability of GO and MK-GO
suspensions in SCPS
In order to illuminate the role of MK particles on the dispersion
and stability state of GO nanosheets in SCPS, the pure GO and also
MK modified GO suspensions with different MK/GO mass ratios
were investigated visually a few minutes after their contact with
SCPS. As can be seen in Fig. 4, GO was agglomerated in all of the
suspensions rapidly. However, based on the appearance of the
samples, the rate of the agglomeration and consequent sedimenta-
tion of MK-GO suspensions was much higher than GO suspension
so that the supernatant of the MK-GO suspensions was approxi-
mately transparent. This observation may be due to the adsorptive
characteristic of the highly negative surface charge of MK particles
in SCPS which can lead to the formation of a positively charged
stern layer consisting of Ca2+ cations [46]. Consequently, Ca2+
cations can interlock MK particles and GO nanosheets through
their mediation effect which is responsible for the formation of
MK-GO cross-links as explained previously by Park et al. [47]. This
way, the agglomeration of GO could be accelerated not only by
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Fig. 4. Visual examination of GO and MK-GO samples in SCPS.

electrochemical double layer compression but also through the To further investigate, the UV–vis spectroscopy was conducted
better screening of the surface charge of GO due to the presence on the samples; the adsorption peak of GO nanosheets was almost
of the adjacent Ca2+ cations [48,49]. zero for all cases. This severe agglomeration could mainly be attrib-

Fig. 5. SEM image of MK-GO suspension in SCPS at low magnification (a) alongside its corresponding elemental distribution maps of (b) Silicon (c) Carbon (d) Calcium (e)
Sodium and (f) Potassium.

7
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
uted to the Ca2+ cations as Zhao et al. [16] stated that only a con-
centration of 2.2 mM of Ca2+ is enough to hinder the suitable dis-
persion of GO sheets. While based on the results of ICP-OES
experiment, the concentration of Ca2+ in the prepared SCPS was
about 19.5 mM. Moreover, the pH values of GO and MK-GO sus-
pensions were 13.25 and 13.15–13.25 (Fig. 4), respectively; which
indicates the negligible effect of the incorporated MK on the con-
centration of OH as the presence of these anions is an obstacle
against the good dispersion of GO nanosheets. Therefore, MK can-
not reduce the concentration of Ca2+ or OH to a considerable
extent at an early age by the pozzolanic reaction.
Additionally, for deep investigating the agglomeration of MK-
GO suspension besides the effects of Ca2+, K+, and Na+ as the main
cations in SCPS on the agglomeration of MK-GO suspension, SEM
imaging along with the elemental mapping analysis were adopted.
Fig. 5 illustrates the SEM micrograph and also the corresponding
elemental maps of the agglomerated MK-GO sample in SCPS. As
can be observed, the existence of the abundant blank dark spaces
in the elemental distribution maps of Silicon (Si) and Carbon (C)
revealed the non-uniform distribution of MK and GO in SCPS,
respectively; which could be evidence of their tendency to be
agglomerated in the high-alkaline environment of SCPS. Moreover,
by comparison of the elemental distribution maps of Ca2+, K+, and
Na+, it could be seen that the accumulation of calcium cations on
Fig. 6. (a) The effect of different PCE/GO mass ratios on the UV–vis spectra of GO in SCPS. (b) The interpolation between the peak absorbance of PCE-GO suspensions in SCPS
for different PCE/GO mass ratios.
Fig. 7. Schematic representation of the arrangement of PCE macro-molecules in PCE-GO suspension: (a) low dosage of PCE (b) moderate dosage of PCE (c) high dosage of PCE.
8
Construction and Building Materials 270 (2021) 121462
the agglomeration sites of MK-GO was significantly more than
potassium and sodium cations. This observation confirmed that
Ca2+ divalent cations are more effective than K+ and Na+ monova-
lent cations in the agglomeration of MK-GO suspension mainly
due to the chemical cross-linking effects of Ca2+ cations [50].
To summarize, based on the obtained results, it can be con-
cluded that the incorporation of MK alone cannot inhibit the
agglomeration of GO nanosheets in high-alkaline cementitious
environments and no significant improvement in the dispersion
and stability of MK modified GO suspension compared with the
pure GO suspension was observed.
3.2. Investigation of the dispersion and stability of PCE-GO and MK-
PCE-GO suspensions in SCPS
Based on the obtained results in the previous section, in order to
ameliorate the dispersion and stability of pure GO and MK-GO sus-
pensions in SCPS, the influence of the incorporation of PCE into the
mentioned suspensions was comparatively evaluated by different
characterizations. Fig. 6(a) depicts the effect of PCE on the peak
absorbance of GO in SCPS. As can be seen, PCE can significantly
improve the dispersion of GO nanosheets in SCPS since,
quantitatively, the peak absorbance of PCE modified GO is very
close to the peak absorbance of GO in water (Fig. 2(b)). As stated
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

previously, PCE macro-molecules can interact with GO through the
covalent bonding between –COO groups of the main chains of PCE
and –COOH groups on the surface of GO [24]. Consequently, PCE
macro-molecules contribute to the prevention of the agglomera-
tion of GO nanosheets mostly due to the steric hindrance effect
that comes from PCE’s side chains [51].
Moreover, as shown in Fig. 6(b), with the increase in PCE/GO
ratio, the peak absorbance of GO drops continuously, which could
be attributed to the formation of micelles that reduce the effective-
ness of using PCE [23]. The schematic illustration of the arrange-
ment of PCE macro-molecules with increasing PCE dosage is
presented in Fig. 7. On the other side, the formation of GO agglom-
erates was observed by Zhao et al. [25] for suspensions with PCE/
GO = 1. Hence, it can be concluded that the appropriate PCE/GO
ratio in PCE-GO suspensions is about 2. Although the results of
UV–vis characterization revealed that the incorporation of PCE

Fig. 8. The effect of different MK/GO mass ratios on the UV–vis spectra of MK-PCE-GO suspensions in SCPS for PCE/GO mass ratio equal to (a) 2 (b) 5 (c) 20 and (d) 40. (e) The
interpolation between peak absorbance for MK/GO mass ratios = 100, 300, 600, and 1000 versus PCE/GO mass ratios.

9
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
Fig. 9. UV–vis spectra over time for (a) PCE-GO and (b) MK-PCE-GO suspensions in SCPS.
Fig. 10. Visual investigation of PCE-GO and MK-PCE-GO suspensions in SCPS after (a) 2 h (b) 3d (c) 7d and (d) 11d since their fabrication.
can ameliorate the dispersion of GO in SCPS, the co-effects of PCE
and MK particles in MK-PCE modified GO suspensions should also
be examined.
Fig. 8(a)-(d) shows the UV–vis spectra of MK-PCE modified GO
suspensions for different PCE/GO and MK/GO mass ratios. As can
be seen, the MK-PCE hybrid has been able to improve the disper-
sion of GO in SCPS in the best possible way. Based on the results
of UV–vis characterization, the MK/GO = 100 can be considered
as the most effective ratio. The interpolations between the absor-
bance peaks for different MK/GO and PCE/GO mass ratios are pre-
sented in Fig. 8(e). It can be seen that unlike the PCE-GO samples in
SCPS, for MK-PCE-GO suspensions, the increase in PCE/GO from 2
to 5 has increased absorbance peaks, but for the PCE/GO ratios
greater than 5, the absorbance peaks have been reduced. Therefore,
the PCE/GO = 5 can be considered as the optimal ratio for MK-PCE-
GO suspensions in terms of the UV–vis absorbance.
In addition, in this study, the stability of PCE-GO and MK-PCE-
GO suspensions in SCPS was examined by measuring their UV–
vis absorption over time. The PCE/GO mass ratio was 5 for both
of the samples while the MK/GO mass ratio equal to 600 was
selected for the second sample as the representative sample of
MK-PCE-GO suspensions. As presented in Fig. 9(a), the absorbance
of the PCE-GO sample after 11 days was declined drastically. Yet, it
can be viewed in Fig. 9(b) that the sample containing MK-PCE-GO
was still stable after 11 days and its absorption was reduced
slightly. The reduction in the absorbance peak for PCE-GO and
MK-PCE-GO suspensions after 3 days was 16.9% and 3.2%, respec-
tively which indicates high stability of MK-PCE-GO suspension in
comparison with PCE-GO at early times. To sum up, MK has
increased the stability of PCE-GO suspension in SCPS and post-
poned its agglomeration and subsequent sedimentation which is
also obvious from the visual investigation’s images shown in
Fig. 10.
10
Construction and Building Materials 270 (2021) 121462
For further investigation of the interaction between the con-
stituents of suspensions, the zeta potential measurements were
conducted on PCE-GO and MK-PCE-GO suspensions in SCPS, and
the results are shown in Table 8. It should be indicated that the
aforementioned suspensions were fabricated initially and then a
sample of their mixture with a moderate pH value was added to
the SCPS.
Based on the former studies [25,52,53], despite the electrostatic
repulsion between the oxygen-containing functional groups of GO
nanosheets and the negatively charged main chain of PCE copoly-
mers, the adsorption of PCE on the surface of GO occurs due to a
huge gain in entropy because of the release of large amounts of
water molecules and ions attached to the backbone and side chains
of PCE copolymers and GO nanosheets. In the Ca2+ loaded environ-
ment of SCPS, the deprotonated carboxylic groups on the backbone
of PCE interact strongly with calcium ions via both complexation
and counter-ion condensation [53]. Moreover, the steric hindrance
mechanism caused by the side chains of PCE stretching into the
SCPS moves the shear plane of the zeta potential further away from
the surface of GO where the zeta potential is close to the isoelectric
point [54]. Herein, the obtained zeta potential value of PCE-GO in
SCPS confirmed that the steric hindrance effect of the adsorbed
PCE on GO is attained practically. The schematic illustration of
Table 8
Zeta potential of PCE-GO and MK-PCE-GO suspensions in SCPS.
Sample name MK: GO mass ratio Zeta potential (mV)
PCE-GO – 2.4 ± 0.4
MK-PCE-GO 100: 1 1.5 ± 0.2
MK-PCE-GO 300: 1 0.5 ± 0.1
MK-PCE-GO 600: 1 1.2 ± 0.1
MK-PCE-GO 1000: 1 4.3 ± 0.8
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
the electrochemical double layer surrounding PCE modified GO in
SCPS is shown in Fig. 11. Besides the zeta potential measurements,
another beneficial experiment for illuminating the influence of PCE
Fig. 11. Schematic illustration of the electrochemical double layer of PCE-GO
suspension dispersed in SCPS at the pH of 13.2.
Fig. 12. Particle size distribution of (a) GO and (b) PCE-GO suspensions in SCPS.
11
Construction and Building Materials 270 (2021) 121462
on dispersion of GO in SCPS was particle size analysis which was
conducted to investigate the average size of the pure GO and PCE
modified GO samples in SCPS. Fig. 12 represents the results of
the particle size analysis. As can be seen, the average size of PCE
modified GO nanosheets noticeably decreased in comparison with
the case of individual GO in SCPS which can be evidence for the
improved dispersion of GO in SCPS due to the presence of PCE
copolymers.
In the case of MK-PCE-GO suspensions in SCPS, the effects of
different MK/GO mass ratios with an identical PCE/GO mass ratio
equal to 5 on their zeta potential values were investigated. Due
to the utilization of this PCE dosage, it could be expected that
PCE copolymers exist in two different forms in SCPS as follows:
1- the adsorbed PCE on the surface of GO which in this case can
lead to the neutralization of the negative charges of GO through
their steric hindrance effect [23,25]; 2- individual PCE with high
anionic charge density due to the deprotonation of the carboxylic
groups that present on their backbones [53]. Also, in this case,
due to the anchoring effect of the negative surface charge of MK
besides the mediation effect of Ca2+ cations, it could be expected
that a double stern layer be formed. With an increase in the
amount of MK, the charge density of the first cationic stern layer,
and consequently its affinity for adsorbing the negatively charged
particles increases significantly. However, it is worth to mention
that in this case, there is a competition between the negatively
charged particles, including PCE modified GO, individual PCE, and
sulfate anions to be adsorbed on the first positively charged stern
layer [48,49]. Actually, due to the steric stabilization and also
charge neutralization of GO by PCE, the interaction between Ca2+
cations and PCE modified GO nanosheets will be significantly
decreased. Therefore, it could be expected that a large number of
positive sites in the first stern layer be occupied by the individual
PCE copolymers, compared with the PCE modified GO nanosheets,
owing to their high tendency for binding and thus forming com-
plexations with Ca2+ cations. Indeed, the formation of these com-
plexations was responsible for the sign change of zeta potential
values from negative to positive [25]. On the other hand, because
of the steric hindrance effects of the both adsorbed individual
PCE and PCE modified GO on the displacement of the shear plane
of zeta potential to a further distance away from the surface of
MK, all of the zeta potential values are close to the isoelectric point
[54,55]. Fig. 13(a) and (b) shows the schematic representation of
the electrochemical double layer of MK-PCE-GO with different
MK/GO mass ratio in SCPS. As a result, it can be deduced that the
incorporation of MK-PCE in the GO suspensions in SCPS results in
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Fig. 13. Schematic illustration of the electrochemical double layer of MK-PCE-GO suspensions with MK/GO mass ratio equal to (a) 100 and (b) 1000 dispersed in SCPS at the
pH of 13.2.

weakening the effectiveness of Ca2+ and other cations in aggrega-
tion and subsequent coagulation of GO nanosheets which is also
obvious from the results of visual investigation and UV–vis charac-
terization. Additionally, to assess the average size of MK-GO and
MK-PCE-GO suspensions in SCPS, the particle size analysis was
performed on the sample with MK/GO mass ratio of 600 which
its results are shown in Fig. 14. As can be seen, in this case, the
average size of the MK-PCE-GO suspension shifts to the lower val-
ues of diameters which can be evidence for the good dispersion of
MK-PCE-GO suspension in SCPS.
The SEM-EDS analysis also revealed the good dispersion mor-
phology of the MK-PCE-GO suspension in the cation loaded envi-
ronment of SCPS. The images of the SEM-EDS characterization
are shown in Fig. 15. Based on the combined results of the SEM
image and EDS spectrum 1, it can be seen clearly that the presence
of well-dispersed GO is detected due to the existence of Carbon (C)
dominant peak. Moreover, Si and Al peaks revealed the presence of
MK particles while the K, Ca and Na peaks were attributed to the
high ionic strength characteristic of SCPS which was in accordance
with the result of ICP characterization (Table 6). Additionally, EDS

Fig. 14. Particle size distribution of (a) MK-GO and (b) MK-PCE-GO suspensions in SCPS.

12
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
Fig. 15. SEM image of MK-PCE-GO suspension in SCPS with 10kx magnification (a) alongside the EDS spectrum 1 (b), corresponding elemental distribution maps of (c) Silicon,
and (d) Carbon of MK-PCE-GO suspension in SCPS.
mapping analysis of Carbon (C) and Silicon (Si) elements revealed
that the number of blank dark spaces, compared with the case of
PCE absence, significantly decreased which confirms that the
MK-PCE modified GO suspensions are not only well dispersed in
SCPS but also uniformly distributed in this high-alkaline
environment.
Heretofore, there was a more emphasis on the investigation of
the effects of different ratios of MK/GO and PCE/GO on the
13
Construction and Building Materials 270 (2021) 121462
dispersion of GO in SCPS; while the ultrasonication treatment is
also a crucial factor for dispersion of nanomaterials such as GO in
aqueous solutions. Therefore, evaluating the effects of different
ultrasonication energies on the dispersion of MK-PCE-GO suspen-
sions in SCPS seems necessary. For this purpose, two series of
MK-PCE-GO suspensions with identical MK/GO and PCE/GO ratios
(600 and 5, respectively) were fabricated with time-controlled and
power-controlled ultrasonication, respectively. Then, their
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
dispersion state in SCPS was characterized using UV–vis
spectroscopy. It is noteworthy to mention that for the time-
controlled suspensions, the ultrasonication power level was set
to 75 W; while, on the other hand, for the power-controlled ones,
the ultrasonication time was maintained at 10 min. The UV–vis
absorption spectra of MK-PCE-GO suspensions in SCPS with differ-
ent ultrasonication time and power levels are shown in Fig. 16(a)
and (b), respectively. Furthermore, Fig. 16(c) and (d) depicts the
effect of ultrasonication energy in terms of time- and power-
controlled ultrasonication on the UV–vis absorbance of MK-PCE-
GO suspensions in SCPS. For each kind of the ultrasonication
treatment, the fitted curve’s formula was determined based on a
non-linear regression analysis of the experimental data. According
to the goodness of fit (R2), it can be seen that the fitted curves are
adequate to predict the trend of the observed data. Based on the
obtained results, it was revealed that at the low ranges of ultrason-
ication energy, the UV–vis absorption increased significantly with
both ultrasonication time and power growth. This could be mainly
due to the ultrasonication separating forces which played a major
role in exfoliation of GO nanosheets [56]. Moreover, with the grad-
ual increase in ultrasonication time and power levels, the UV–vis
absorptions also increased until they reached a peak, and after-
ward, a decrease in absorption was observed in both graphs.
Indeed, this decline corresponds to the effects of ultrasonication
scissoring forces dominating separating forces at relatively high
ultrasonication energies [56–58] which can lead to a smaller parti-
cle size of GO nanosheets [59] and also damage to their structure
Fig. 16. UV–vis absorption spectra of MK-PCE-GO suspensions in SCPS with different (a) ultrasonication time and (b) ultrasonication power levels. The variation of peak
absorbance of MK-PCE-GO suspensions in SCPS with different amounts of ultrasonication energy in (c) time-controlled and (d) power-controlled ultrasonication treatment.
14
Construction and Building Materials 270 (2021) 121462
[60]. However, the observed reduction in the absorbance of
power-controlled suspensions was more than the time-controlled
ones, which implied significant deterioration effects of the high
ultrasonication power levels, compared with the time levels, as
indicated in the previous studies [56,61]. As a result, it can be
concluded that there is a compromise between ultrasonication
separating forces and scissoring ones in both time- and power-
controlled ultrasonication, which can improve or degrade the
dispersion state of GO depending on the value of ultrasonication
energy. According to the aforementioned mechanism, the
optimum range of ultrasonication energy for time- and power-
controlled ultrasonication treatments are also shown with yellow
and green regions, respectively.
3.3. Mechanical properties and ultrasonic pulse velocity measurements
of cement paste samples
To verify the results of dispersion experiments and also for
investigating the effects of well-dispersed MK-GO compared to
pure GO on mechanical properties of cement composites, the com-
pressive and flexural strength tests were conducted on the cement
composite samples. The main reinforcing mechanisms of GO
nanosheets in the literature are including acceleration of the
cement hydration rate, modification of the pore structure of
cement composites, hindering the spreading of fine cracks and
facilitation load transfer at the intersection of GO-host matrix
[62–65]. Also, principal mechanisms for the effect of MK on
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Fig. 17. Mechanical strengths of cement paste samples: (a) Compressive strength and (b) Flexural strength. (c) Flexural load–displacement curves of cement paste samples at
curing age of 28 days.

Table 9 reinforced samples are promoted by 10.4%, 6.4%, 12.6%, and

Maximum load, flexural modulus, and relative flexural toughness of cement paste 13.4% after 3, 7, 28, and 90 days of curing, respectively compared
samples. with PCE-GO-Cement samples. On the other hand, the flexural
Sample Maximum Flexural Flexural strengths of the specimens are plotted in Fig. 17(b). As can be seen,
load (N)/increase modulus (GPa)/ toughness/ the flexural strength of MK-PCE-GO-Cement samples after 90 days
rate (%) increase rate (%) increase rate (%) of curing has been improved by 31.4%, 24.2% and 14.4% in compar-
PCE-Cement 337.2/0 0.484/0 1/0 ison with PCE-Cement, MK-PCE-Cement and PCE-GO-Cement sam-
MK-PCE-Cement 356.3/5.7 0.518/7 1.06/6 ples, respectively. Based on the obtained results, it can be deduced
PCE-GO-Cement 420/24.6 0.663/37 1.30/30 that the enhancing effect of well-dispersed MK-GO on the mechan-
MK-PCE-GO-Cement 459.3/36.2 0.725/49.8 1.42/42
ical properties of cement paste samples was significant. To further
investigate the reinforcing effects of MK-GO, compared to pure GO
as well as MK alone, on the flexural modulus and toughness of
cement-based composites are the acceleration of the cement
cement paste samples, the flexural load–displacement curves of
hydration process, the filler effect of MK particles, and the poz-
the plain sample besides the samples containing MK-GO, GO and
zolanic reaction between MK and Ca(OH)2 which produces sec-
MK at the curing age of 28 days are presented in Fig. 17(c). The
ondary calcium silicate hydrate (C-S-H) gel [66]. In this research,
flexural modulus was calculated based on the following equation:
in the case of MK-GO modified samples, due to the hybrid usage
of GO and MK, all the aforementioned mechanisms are probable 3
l
to take place and could lead to strengthening the samples. E¼m 3
ð2Þ
4:b:d
The mean values of the mechanical strengths of cement paste
samples are exhibited in Fig. 17. Fig. 17(a) demonstrates the com- where m is the slope of the tangent to the initial straight-line por-
pressive strengths of PCE-Cement, MK-PCE-Cement, PCE-GO- tion of the load–displacement curve; l is the support span (60 mm);
Cement and also MK-PCE-GO-Cement samples. The compressive b and d are the sample width and depth (15 mm each), respectively.
strengths of both MK-PCE-GO-Cement and PCE-GO-Cement Moreover, in this study, the flexural toughness of each sample was
samples were significantly increased compared to both of the calculated based on the area under the corresponding load–dis-
PCE-Cement and MK-PCE-Cement samples, especially at the early placement curve to the point of fracture and is presented as the rel-
days. Besides, the values of the compressive strength of MK-GO ative value to the plain sample. Table 9 lists the maximum flexural
15
K. Amini, A. Ghasemi, S. Soleimani Amiri et al. Construction and Building Materials 270 (2021) 121462

Fig. 18. Ultrasonic pulse velocity measurements of cement paste specimens.

Fig. 19. Mechanical strengths of cement mortar samples: (a) Compressive strength and (b) Flexural strength. (c) Flexural load–displacement curves of cement mortar
samples at curing age of 28 days.

16
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
load, modulus, and nominal toughness of cement paste samples. It
can be seen that the flexural modulus and toughness values of the
MK-GO reinforced sample have increased by 49.8% and 42%, respec-
tively, compared with that of the plain sample, which were more
than the measured enhancements in the flexural modulus and
toughness of the both GO or MK modified samples. Generally, this
improvement is attributed to the nucleation effects of GO
nanosheets [62] besides the better load-transfer efficiency with
the presence of uniformly dispersed MK-GO hybrid in the cement
matrix, due to the incorporation of PCE copolymers [26] as observed
in the SEM image of MK-PCE-GO in SCPS (Fig. 15). Moreover,
another contribution in the MK-GO modified sample can be devoted
to the pozzolanic activity of MK particles which can lead to the for-
mation of secondary C-S-H gel, thus resulting in a denser
microstructure and consequently higher load-bearing capacity [66].
Furthermore, the effect of well-dispersed MK-GO in comparison
with pure GO or MK alone on the microstructure refinement of
cement composite samples was investigated using the ultrasonic
pulse velocity test. The value of UPV in cement composites mainly
corresponds to both structural homogeneity and density of the
cement composite and the density is reversely proportional to
the value of UPV [67]. On the other hand, the structural non-
homogeneity, such as pores and cracks, can disturb ultrasonic
pulse propagation through the cement composite and conse-
quently decrease its velocity [63]. Based on the mass and dimen-
sions of the mixes of cement paste samples, the density of the
MK-GO reinforced sample and also the GO or MK incorporated
samples was similar to that of the plain sample which was approx-
imately equal to 1.9 g/cm3. This could be due to the extremely low
Table 10
Maximum load, flexural modulus, and relative flexural toughness of cement mortar
samples.
Sample Maximum Flexural
load (N)/ modulus (GPa)/
increase rate (%) increase rate (%)
PCE-Cement 2667/0 1.11/0
MK-PCE-Cement 2773/4 1.15/3.6
PCE-GO-Cement 3165/18.7 1.17/5.4
MK-PCE-GO-Cement 3505/31.4 1.23/11
Fig. 20. Ultrasonic pulse velocity measurements of cement mortar specimens.
Construction and Building Materials 270 (2021) 121462
concentration of the utilized GO and similar density between GO
sheets and cement composites [68] as well as the small amount
of metakaolin in MK-PCE-Cement and MK-PCE-GO-Cement sam-
ples. Therefore, in this case, it can be concluded that the result of
the UPV test was mainly affected by the structural homogeneity
of cement composites. Fig. 18 shows the UPV test results of cement
paste specimens. It is inferred that the UPV values are increased
over time up to 90 days due to the progress of the cement hydra-
tion process and this increase is relatively higher in the early days
of curing. The UPV values for MK-PCE-GO-Cement specimen were
10.1%, 10.7%, 5.0%, and 7.5% more than PCE-Cement after 3, 7, 28,
and 90 days, respectively. This enhancement could be ascribed to
the pore refinement and also the acceleration of the cement hydra-
tion process caused by GO and MK particles [51,63,69]. Besides, the
UPV values for MK-PCE-GO-Cement showed a slight enhancement
compared with the PCE-GO-Cement samples. Also, from the
observed trend in the UPV values of the MK-PCE-Cement and
PCE-GO-Cement samples, it can be concluded that the incorpora-
tion of GO has improved the UPV values of the cement paste sam-
ples more effectively than MK at all ages.
3.4. Mechanical properties and ultrasonic pulse velocity measurements
of cement mortar samples
Similar to the case of cement paste, the mechanical strength
and ultrasonic pulse velocity tests were also conducted on the
cement mortar specimens. The mechanical strengths of cement
mortar samples are presented in Fig. 19. As can be viewed in
Fig. 19(a), the compressive strength of the MK-PCE-GO-Cement
sample is improved by 53.4%, 52.7%, 35.4%, and 22.3% in compar-
ison with the PCE-Cement sample after 3, 7, 28 and 90 days,
respectively. Also, the compressive strengths of MK-GO incorpo-
rated samples are increased compared to MK-PCE-Cement and
Flexural PCE-GO-Cement samples at all ages. Fig. 19(b) shows the flexural
toughness/ strengths of cement mortar samples. It can be seen clearly that
increase rate (%)
the flexural strength for the MK-PCE-GO-Cement sample is more
1/0 than the reference sample at all times. Furthermore, the flexural
1.11/11
strengths values for MK-GO modified samples compared to PCE-
1.29/29
1.42/42 GO-Cement samples were enhanced by 10.0%, 6.1%, 11.2%, and
8.8% after 3, 7, 28, and 90 days, respectively. Also, the flexural
17
K. Amini, A. Ghasemi, S. Soleimani Amiri et al.
load–displacement curves of the plain and MK modified mortar
samples besides the samples reinforced by individual GO and
MK-GO at the curing age of 28 days are shown in Fig. 19(c). It is
noteworthy to mention that in this case; the flexural modulus
was also calculated based on the same Eq. (2) where the value of
m for each sample was determined according to the corresponding
load–displacement curves of cement mortar samples. Moreover, in
this case, the values of l, b, and d were equal to 120 mm, 40 mm,
and 40 mm, respectively. The values of maximum load, flexural
modulus, and toughness are given in Table 10. As can be seen,
the flexural modulus and toughness of the mortar samples con-
taining MK-GO were improved by 11% and 42%, respectively, com-
pared with that of the plain mortar sample; while the
enhancement in flexural modulus and toughness of GO reinforced
sample relative to the plain sample was equal to 5.4% and 29%,
respectively. Moreover, the incorporation of MK led to a slight
increase in the flexural modulus and toughness of the cement mor-
tar samples. The desirable mechanical properties of the MK-PCE-
GO-Cement mortar sample can be mainly due to the reinforcing
effects of the well-dispersed MK-GO in cement matrix, similar to
the case of cement paste samples.
In the case of cement mortar specimens, the mass and dimen-
sions measurements revealed that there was no significant differ-
ence between the densities of cement mortar samples. It is
noteworthy to mention that the density of the mixes of cement
mortar samples was approximately equal to 2.1 g/cm3. Therefore,
in this case, similar to the cement paste samples, density had a
negligible effect on the result of the UPV test. The UPV test results
of cement mortar specimens are depicted in Fig. 20. The UPV val-
ues for the MK-PCE-GO-Cement sample compared to the PCE-
Cement sample were increased by 2.4%, 2.7%, 5.6%, and 7.0%,
respectively. In addition, the higher UPV values in MK-PCE-GO-
Cement samples against MK-PCE-Cement and PCE-GO-Cement
samples up to 90 days could be as a consequence of the co-
effects of well-dispersed MK-GO on the structural homogeneity
and pore refinement of cement mortar specimens.
In summary, based on the outcomes of the dispersion experi-
ments as well as the mechanical strength tests and UPV measure-
ments that were conducted in the current study, the incorporation
of MK-PCE hybrid not only can improve the dispersion and stability
status of GO in alkaline cementitious solutions but also makes GO
contribute more to the mechanical enhancement and pore refine-
ment of cement composites. Hence, the profound investigation of
the microstructure and transport properties of the cement com-
posites modified by MK-PCE-GO could be the subject of future
studies.
4. Conclusions
In this study, firstly, the ability of MK particles to ameliorate the
dispersion of GO nanosheets in SCPS was evaluated. Next, the influ-
ence of MK-PCE hybrid, compared to PCE alone, on dispersion
behavior of GO was comparatively investigated through a combi-
nation of experiments. Finally, to certify the outcomes of disper-
sion characterizations in the macroscopic level, the mechanical
properties and ultrasonic pulse velocities of the corresponding
mixes of cement composites were measured and compared with
each other. The main findings are summarized as follows:
1. The results of visual examinations implied the severe agglomer-
ation and sedimentation of pure GO and MK-GO suspensions in
SCPS which was in accordance with the very low UV–vis peak
absorptions of GO and MK-GO suspensions. Moreover, the com-
parison of pH values of GO and MK-GO suspensions showed
that MK had a negligible influence on the concentration of
18
Construction and Building Materials 270 (2021) 121462
OH and Ca2+ ions as the main GO agglomeration agents. Also,
the non-uniform distribution of Carbon and Silicon elements
which was revealed by EDS mapping analysis was another evi-
dence for the agglomeration of MK-GO hybrid in SCPS.
2. Based on the visual investigations coupled with UV–vis experi-
ments in SCPS, GO nanosheets in PCE-GO and MK-PCE-GO sus-
pensions had the desired dispersion. However, the
incorporation of MK-PCE hybrid, compared to the PCE alone,
had a significant favorable effect on the stability of GO
nanosheets. This observation is attributed to the anchoring
characteristic of the negative surface charge of MK particles
besides the steric hindrance effect of PCE’s side chains which
can reduce the possibility of the interaction between GO
nanosheets and Ca2+ cations. Also, the significant reduction in
the average size of MK-PCE modified GO suspension, compared
to the MK modified one, confirmed the good dispersion of MK-
PCE-GO suspension in SCPS. Moreover, no obvious dark spaces
were observed in the MK-PCE-GO elemental distribution maps
of Carbon and Silicon which revealed that the distribution of
GO and MK particles is uniform. Furthermore, in the case of
MK-PCE-GO suspensions, the optimal range of the ultrasonica-
tion energy was approximately in the range of 25–40 KJ based
on the both power and time-controlled ultrasonication
treatments.
3. For cement paste and mortar samples containing MK and GO,
the mechanical properties, such as compressive and flexural
strength, flexural modulus, and toughness were enhanced in
comparison with the both of GO or MK modified as well as
the reference samples. Also, the ultrasonic pulse velocity mea-
surements showed an increase in UPV values for the samples
modified by MK and GO at all times compared to the other sam-
ples. The improvement in mechanical and also microstructural
properties of the MK-GO modified samples could be ascribed
to the reinforcing effects of both GO nanosheets and MK parti-
cles besides the nucleation effects of GO and pozzolanic activity
of MK which is obtained by proper dispersion of MK-GO hybrid
through the incorporation of PCE.
CRediT authorship contribution statement
Kasra Amini: Writing - original draft, Visualization, Investiga-
tion. Ali Ghasemi: Writing - original draft, Visualization, Investiga-
tion. Siavash Soleimani Amiri: Writing - original draft,
Visualization, Investigation. Sajjad Mirvalad: Supervision, Concep-
tualization, Methodology, Writing - review & editing. Asghar
Habibnejad Korayem: . : Supervision, Conceptualization,
Methodology.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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