Construction and Building Materials 259 (2020) 119687

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Construction and Building Materials

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

High performance cementitious nanocomposites: The effectiveness of

nano-Graphite (nG)
Mehdi Chougan a,c, Emanuele Marotta a, Francesca R. Lamastra a, Francesco Vivio a,
Giampiero Montesperelli a, Ugo Ianniruberto b, Seyed Hamidreza Ghaffar c, Mazen J. Al-kheetan d,
Alessandra Bianco a,⇑
a
University of Rome ‘‘Tor Vergata”, Dipartimento Ingegneria dell’Impresa ‘‘Mario Lucertini”, Consortium INSTM RU ‘‘Roma Tor Vergata”, Via del Politecnico, 00133 Roma, Italy
b
University of Rome ‘‘Tor Vergata”, Dipartimento di Ingegneria Civile e Ingegneria Informatica (DICII), Via del Politecnico, 00133 Roma, Italy
c
College of Engineering, Design and Physical Sciences, Brunel University London, Uxbridge, Middlesex UB8 3PH, United Kingdom
d
Department of Civil and Environmental Engineering, College of Engineering, Mutah University Mutah, Karak 61710, P.O. BOX 7, Jordan

h i g h l i g h t s

Nano-Graphite cement composites are high-performance multifunctional materials.

Smooth workability loss of the fresh admixtures.

Improved density and mechanical strength.

Enhanced damping, electrical and thermal conductivity at the lowest dosage.

Reduced water permeability and chloride penetration.

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

Article history: In this study an extensive experimental campaign has been conducted on mortars modified with nano-
Received 20 December 2019 Graphite (nG) aimed to assess the properties of the resulting nanocomposites in terms of density,
Received in revised form 27 May 2020 microstructure, flexural and compressive strength, damping ratio, thermal and electrical conductivity.
Accepted 29 May 2020
Permeability properties were also investigated in terms of initial surface absorption, water contact angle,
volume of permeable voids and chloride ion diffusion.
Premixed mortars have been modified with different dosages of commercial nG, i.e. 0.01%, 0.1%, or 0.2%
Keywords:
by weight of cement. The rheological behavior of the fresh admixtures has been investigated. Specimens
Cementitious materials
Nano-graphite
were casted in bars and hardened in water for 7, 14 or 28 days. At 28 days all samples showed enhanced
Rheology density (i.e. up to 16%) and mechanical properties (i.e. up to 30%) combined to remarkable decreased
Microstructure overall permeability. The lowest dosage of nG (i.e. 0.01% by weight of cement) resulted in cement
Mechanical properties nanocomposites with the highest increase in damping ratio, electrical and thermal conductivity, 68%,
Permeability 30% and 55%, respectively.
Damping ratio Crown Copyright Ó 2020 Published by Elsevier Ltd. All rights reserved.
Electrical resistivity
Thermal conductivity

1. Introduction decades, several nanofillers (such as nano-TiO2, nano-SiO2, nano-

In the last decade, the world faced a rapidly growing interest
toward cementitious materials such as mortar and concrete; how-
ever, the application of these materials is limited by their quasi-
brittle behavior, low toughness, and poor tensile strength [1].
These limitations encouraged scientists to improve their properties
by combining nanotechnology to construction materials. In the last
⇑ Corresponding author.
E-mail address: bianco@stc.uniroma2.it (A. Bianco).
clays and carbon nanotubes) have been investigated aimed to
obtain cement-based nanocomposites characterized by improved
mechanical and physical properties combined with enhanced
durability [2–4].
More recently, the unique and superior properties of Graphene-
Based Materials (GBMs) demonstrated to enhance the properties of
cementitious nanocomposite at such an extent that they might
reach high, and even ultrahigh, mechanical and physical perfor-
mances [5].

https://doi.org/10.1016/j.conbuildmat.2020.119687
0950-0618/Crown Copyright Ó 2020 Published by Elsevier Ltd. All rights reserved.
2 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
In the near future, the resulting multi-functional nanocompos-
ites are expected to offer novel applications in the field of civil
engineering, such as inductive wireless charging roads, underfloor
heating, underground power transmission lines, high-speed train
lines, high-voltage transmission pipelines and de-icing roads
[6,7]. Interestingly, the enhanced electrical conductivity might also
induce self-sensing properties, allowing smart construction mate-
rials to identify and monitor the initiation of defects within the
structure [8]. Moreover, high performance cementitious materials
able to absorb vibration energy are particularly valuable for big
structures, such as high buildings, concrete bridges and high-
speed train railways, subject to extreme environmental conditions
(i.e. earthquake and high-speed winds) [9,10].
The objective of this study is to assess the overall impact of
commercial nano-Graphite (nG), previously fully characterized,
on the properties of mortars loaded with different amounts of
nanofiller (i.e. 0.01%, 0.1%, and 0.2% by weight of cement). The
interest toward nano-Graphite as nanofiller is based on its unique
features, including (i) easy production process from natural gra-
phite, compared to other graphene-based materials; (ii) low-
oxygen multilayed graphene structure characterized by high ther-
mal conductivity (about 5300 W/m.K) and electron mobility (about
15,000 cm2V1s1) that enables the enhancement of the thermal
and electrical properties of the resulting nanocomposites [11,12];
(iii) superior nano-scale effect that reflects in improved density
and mechanical performance of the modified host matrices, as
robustly proved by the effective incorporation of nG in various
thermoplastic and thermoset polymers [13–15]. More recently,
nano-Graphite demonstrated also an excellent candidate for the
developing of high performance cementitious nanocomposites
[16].
Rheology, mechanical properties (i.e. flexural and compressive
strength), physical properties (i.e. damping ratio, thermal and elec-
trical conductivity) along with permeability features (i.e. initial
surface absorption, water contact angle, volume of permeable
voids and chloride ion diffusion) have been investigated.
Presently, to the best of our knowledge, a fully comprehensive
study on nano-Graphite cementitious composites has not been
previously reported. Moreover, it is worthy to mention that only
few researches investigated the effectiveness of graphene-based
cementitious composites to the exposure to aggressive environ-
ments [17,18].
2. Materials and methods
2.1. Materials: Mortar and nano-Graphite (nG)
A M5 class EN 998-2 premixed dry mortar consisting mainly of
Ordinary Portland Cement (OPC), graded sands, and hydrated lime
was employed. In accordance with ASTM C109, the composition by
weight is the following: 1 part of cement, 2 parts of sand and 0.75
parts of hydrated lime. It is well known that the presence of
hydrated lime improves the workability of mortars, making the
product easier to handle for unprofessional users [19,20]. Accord-
ing to the producer, the maximum particle size of the chosen pre-
mixed mortar is below 3 mm.
The employed carbon nanofiller was a free-flowing dry powder
of nano-Graphite platelets (Grade Nano99 by Asbury Carbons, New
Jersey, USA), characterized by the producer as follows: primary par-
ticle size below 100 nm, specific surface area (SSA) 402 m2/g, car-
bon content more than 97.5% (Loss on Ignition, LOI), and Lamella
Thickness Index (LTI) between 6 and 7 nm.
Phase analysis of the nG powder was performed by X-ray
diffraction (XRD) (Philips X’Pert Pro), in the following conditions:
CuKa radiation, k = 1.5405600 Å, 2h = 5–80°, step size = 0.020°,
time per step = 2 s, scan speed = 0.01°/s. The average size of crys-
tallites was evaluated from the full width at half-maximum
(FWHM) of the diffraction peak at 2h 26.57° corresponding to the
{0 0 2} family of lattice planes of hexagonal graphite (JCPDS 23-
0064), by means of the Scherrer’s equation (1):
Kk
sðhklÞ ¼
bcosh
where K is the shape factor equal to 0.9, k is the wavelength of the
CuKa radiation, b is FWHM (in radians) which is corrected for the
instrumental broadening (b0 = 0.00139 rad) and h is the Bragg angle.
The number of graphene layers (N) was evaluated by Eq. (2) [21]:
N ¼ sð002Þ =dð002Þ ð2Þ
where s(0 0 2) is the thickness of the nanographite platelets calcu-
lated by the Scherrer’s equation, and d(0 0 2) is the interlayer dis-
tance of {0 0 2} family of lattice planes.
The microstructure of the as-received nanofiller was investi-
gated by means of Scanning Electron Microscopy (SEM) (FE-SEM,
LEO Supra 35, Germany). A tiny amount of sample was dispersed
in acetone, a couple of droplets placed on the microscope stub
and air dried at room temperature.
2.2. Preparation and rheological behavior of the fresh admixtures
According to the producer’s indications, the control sample was
prepared adding 18% wt of water to the EN-998-2 premixed mor-
tar. For nanocomposite admixtures, the as-received nanofiller was
dispersed in water for 30 min by means of ultrasonic processor (VC
750, Sonics and Materials, USA) and then added to the cement-based
mixture. The mortar was modified with 0.01, 0.1 or 0.2% (by weight
of cement) of nano-Graphite, the obtained samples being herein
designed as nG-0.01, nG-0.1, and nG-0.2, respectively. It should
be mentioned that, prior to the preparation of the cementitious
admixtures, the ultrasound exposure of nG water suspensions
was examined at different times (i.e. 5 to 40 min). After 24 h, all
the suspensions ultra-sonicated for at least 30 min did not show
visible sediment. A similar dispersion procedure has also being
proposed by Le et al. [22].
Fresh admixtures were stirred for 5 min at 500 rpm in accor-
dance to ASTM C305-06 by means of a mechanical stirrer (Eurostar
digital IKAÒ-Werke, Germany) equipped with a spiral stirrer
IKAÒ-Werke (Germany). Rheology measurements of fresh mortars,
were carried out using a KinexusLab + rheometer (Malvern Instru-
ments Ltd., UK) equipped with rSpace software (Malvern Panalytical
Ltd, UK).
Rheology test of fresh nG-engineered admixtures was per-
formed immediately after the mechanical mixing. Samples were
poured into a cylindrical plastic jar (diameter about 12 cm), shear
stress (s) and apparent viscosity (gp) were measured versus the
shear rate (c), the latter ranged between 5 s-1 and 100 s1 over
10 intervals. Two fitting models, i.e. Bingham model (BM) and Her-
schel–Bulkley model (HB), were employed to evaluate the rheolog-
ical parameters. In order to avoid an incorrect evaluation of shear
stress due to the pseudoplastic behavior of the fresh mortar, only
the modified Bingham model was considered [23–26].
2.3. Preparation and characterization of the hardened nanocomposites
According to the standard ASTM C348-02, prismatic samples of
size 40x40x160 mm were casted in a steel mold, mechanically
vibrated (Retsch, Germany) for 3 min, and kept at room tempera-
ture under a wet towel for 24 h. Samples were finally demolded
and immersed in water at room temperature for 7, 14, or 28 days.
A control sample cured at 200 days was also cast for the sake of
 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
comparison with the cementitious nanocomposites at early ages
(i.e. 7, 14 and 28 days). The idea is to eventually assess, on the basis
of the literature, the acceleration of the hydration process resulting
in increased density and mechanical strength already at early ages
[27,28].
The following tests have been performed on the resulting hard-
ened samples:

Density has been calculated by weight and size measurements
by means of a digital caliper and an analytical balance
(Mettler-Toledo Ltd.);

Flexural and compressive strength were determined in accor-
dance, respectively, to ASTM C348-02 and ASTM C349-02 stan-
dard. MTS (USA) machine equipped with a 100 kN load cell and
a Matest machine (Italy) equipped with a 3000 KN load cell were
employed for three-point bending and compressive test, respec-
tively, latter tests have been performed at 0.1 mm/min load
rate.

Microstructure after 28 days was investigated by means of Scan-
ning Electron Microscopy (FE-SEM, LEO Supra 35, Germany) on
samples (approximately 5x5x5 mm) obtained out of the bars
previously undergone to the compressive test. Since samples
have to be completely dried to stop the hydration process and
‘‘freeze” the microstructural features at 28 days, specimens
were oven dried at 110 °C for 3 days, stored in ethanol [29–
31], and finally gold coated by sputtering (EMITECH K550X sput-
ter coater, Quorum Technologies Ltd., UK).

Damping ratio was determined following the ASTM C 215 stan-
dard. Prismatic samples of 40x40x160 mm were excited in a
transverse mode of vibration with a metallic rigid impactor
(hammer). The samples were held on two soft rubber supports
in which they could freely vibrate in all vibration modes. Since
the damping capacity of cementitious materials is strictly
dependent on the content of water trapped within the porosity
network [32], samples were immediately tested after the
extraction from the water bath. The accelerometer, operating
at a frequency range from100 to 10000 Hz, was located exactly
in the position specified in the ASTM C215 standard. The damp-
ing ratio was calculated as the following Eq. (3) (Fig. 1).
1 Um
n¼ :Ln  100
2pn U mþn
where: Um: amplitude of a selected peak, Um + n: amplitude of a
peak after m cycles, n: number of cycles between the two successive
positive peaks.
Fig. 1. Amplitude versus time graph for logarithmic decrement measurements.
3
In this study, MATLAB software was utilized to process the data.
Fast Fourier Transform (FFT) and Frequency Response Function
(FRF) were utilized for data processing.
Since respond curves may not be smooth enough, the Butter-
worth filtering in Band path response type was dedicated to elim-
inate the effects of noise and unwanted frequencies. After
excitation, each component of the cementitious composite
absorbed part of the vibration energy.

Initial surface absorption test (ISAT) was assessed in accordance
with BS 1881-208:1996. For each composition, 3 cubic samples
100x100x100 mm were cast and cured for 28 days. After curing,
samples were oven-dried at 105 ± 5 °C for 24 h. In order to seal
the samples top-surface, a circular cap (approximately 200 cm2)
was placed onto the cubic samples. Then, distilled water was
fed from the reservoir through the cap to penetrate the mortar
surface. After closing the reservoir flow, the water absorption
rate of samples was measured by monitoring the water dis-
placement along the capillary tube. The initial surface absorp-
tion rate was calculated by the equation (4) after 10, 30 and
60 min [33,34]:
60
f ¼  D  0:01 ð4Þ
t
where: F: initial surface absorption rate (ml/m2.s), D: number of scale
divisions during the test,t: testing time period (s).

Water contact angle test was performed using a video-optical
device (Attension Theta, Biolin Scientific, Germany). Since the sur-
face roughness might compromise the accuracy of the result,
the 100  100  20 mm samples after 28 days of curing were
polished and rectified with silica grinding paper. Then, a droplet
of distilled water (approximately 2 ml) was dropped off onto the
polished surface. The angle between the droplet surface and the
sample surface was measured after 5 s and considered as the
water contact angle [35,36]. For the sake of accuracy, ten differ-
ent zones for each specimen have been considered.

Permeable porosity was evaluated by means of boil-water satu-
ration (BWS) technique, following the ASTM C 642. Three pris-
matic specimens were tested for each composition. After
28 days, samples were dried in oven for 48 h at 110 °C and
ð3Þ
weighted to determine the oven-dry mass. It is worthy to men-
tion that samples have to be oven dried between 100 and 110 °C
for at least 24 h. Specifically, our samples needed two cycles of
24 h to be considered ‘‘dry samples”, i.e. a mass difference
4 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
between the two cycles lower than 0.5%. Samples were then
submerged in water for 48 h and weighted again to determine
the saturated mass after immersion. Finally, samples were
immersed in boiling water for 5 h and then cooled down to
room temperature to determine the saturated mass after boiling.
The volume of permeable voids has been calculated according
to the Eq. (5):
Volumeofpermeablevoidsð%Þ ¼ ½ðC  AÞ=ðC  DÞ  100
where: A: mass of oven-dried sample in the air (g) B: mass of
surface-dry sample in the air after immersion (g) C: mass of
surface-dry sample in the air after immersion and boiling (g) D:
apparent mass of sample in water after immersion and boiling (g).

Salt ponding test was carried out following the BS 14629:2007
with some modifications. In this test, three cubes of dimension
100x100x100 mm were cast and immersed in water for 28 days
and finally oven-dried for 24 h. As shown in Fig. 2, a 15 mm
height wooden dam was used to maintain the specimens fully
immersed in a 5% wt NaCl water solution. Samples were ‘‘ex-
posed” to the saline solution for 30 days; the chloride content
was then determined as follows: (a) samples were oven-dried
for 24 h and then drilled at different depths (i.e. 5, 10, 15, 20
and 25 mm); (b) for each depth the resulting debris were col-
lected; (c) the content of chloride ions was determined by titra-
tion with a silver nitrate water solution (0.02 M) according to
the Eq. (6) [37–39]:
ChlorideContentð%Þ ¼ 3:545  F  ðV2  V1Þ=m
where, F: molarity of the silver nitrate water solution, V2: ammo-
nium thiocyanate solution volume used in the blank titration
(ml), V1: ammonium thiocyanate solution volume used in the titra-
tion (ml), M: sample mass (g).

Electrochemical Impedance Spectroscopy (EIS) was carried out on
40  40  160 mm bars hardened for 7, 14, or 28 days by means
of uniaxial two-point electrode method. This test aims to eval-
uate the effect of different amounts of nano-Graphite on the
electrical resistivity of the cement-based nanocomposites in
the steady state condition. EIS tests (VMP3, BioLogic Science
Instruments, France) were performed by applying an alternate
signal 20 mV in amplitude in a frequency range 10 mHz-100
KHz. The resistivity was calculated from Z (i.e. the highest real
resistance value), according to Eq. (7) [40–43]:
Fig. 2. Experimental set-up for salt ponding test according to BS 14629:200.
R:S
q¼ ð7Þ
L
where, R is the sample resistance, S is the samples cross section and
L is the distance between the two electrodes;

Thermal conductivity tests were carried out by means of a heat
flow meter (Lasercomp Fox 200, Laser Comp’s Inc) in accordance
with ASTM C 518 and EN 12667 (Fig. 3). For each formulation,
ð5Þ
three different samples of 100 100 20 mm hardened for
28 days were placed between two parallel plates at 0 °C and
20 °C, respectively the cold and the hot plate. The results were
then obtained using the ‘‘WinTherm32” software.
In Fig. 4 are resumed all the experimental techniques employed
to in this study to fully characterize the carbon nanofiller and the
resulting cement nanocomposites in terms of microstructure,
mechanical properties, physical properties and permeability.
Statistical evaluation was carried out by the means of
Ò
Minitab 14 statistical software to summarize the output data with
the standard deviation.
3. Results and discussion
3.1. Characterization of nano-Graphite (nG)
The Raman spectrum of the nanofiller (Fig. 5a) showed the three
characteristic bands around 1321 cm1 (D band), 1580 cm1 (G
band), and 2700 cm1 (2D or G’ band) (Fig. 5a). The D band has to
ð6Þ
be assigned to the ‘‘disorder” associate to either the carbon lattice
edges or to the presence of impurities within the aromatic
domains, the G band represents the in-plane vibration ofsp2
bonded carbon atoms, and the 2D (or G’) band related to the num-
ber of layers and, thus, to the thickness of the carbon
nanostructure.
The X-ray diffraction pattern of nG (Fig. 5b) shows the charac-
teristic peaks of the hexagonal graphite (H) (JCPDS 23-0064) along
with two weak peaks at 2h 43.48° and 46.37° due to (1 0 1) and
(0 1 2) reflections of the rhombohedral graphite phase (R) (JCPDS
26-1079) [44]. The main peak of rhombohedral graphite (i.e. d
(003) reflection) is located at 2h 26.62°, nearby the main peak of
hexagonal graphite at 2h 26.57° associated to the (0 0 2) reflection.
The rhombohedral phase is a thermodynamically unstable allotro-
pic form of graphite with an ABCABC stacking sequence of layers; it
usually coexists with the main hexagonal phase and it is produced
 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
Fig. 3. Experimental set up for thermal conductivity measurements.
by shear deformation of hexagonal graphite [45]. The interlayer
distance d (0 0 2), the thickness of nG (i.e. s(0 0 2)) and the number
of graphene layers (N) evaluated from XRD data are 0.335 nm,
31 nm and 92, respectively. The herein evaluated thickness of
nanographite (31 nm) resulted 5 times larger than that one
reported by the supplier (6–7 nm). However, since both H (0 0 2)
and R (0 0 3) reflections contribute to the peak located at 2h
26.57°, the values of both s(0 0 2) and N might not be accurately
determined [27].
Fig. 4. Characterization chart of nanofiller (nG) and cement-based nanocomposites.
5
In Fig. 5c, SEM micrographs at different magnification of the as-
received nanofiller are reported. As expected, micro-sized agglom-
erates generated from the exfoliation of expanded graphite flakes
are observed due to the high tendency of the nano-platelets to
re-bind each other through Van der Waals secondary bonds. Com-
position, size, thickness, and specific surface area (SSA) of as-
received nG, as furnished by the producer, have been resumed in
Table 1. According with several studies, exfoliated nG platelets
are made up of a multilayer net-like structure of carbon–carbon
hexagonal plane, with lateral size between 0.35 and 100 nm,
nanoscale thickness and high specific surface area [46–48].
3.2. Rheology of fresh nG-modified admixtures
In order to investigate the actual effect of the nanofiller on the
rheological behavior of the fresh cementitious admixtures, a flow
curve was recorded for each admixture. Results of the rheological
tests are presented in Table 2 and Fig. 6a–b.
Fresh cement-based mixtures are non-Newtonian fluids and it
is well known that the typical flow curves follow the modified
Bingham model [29], each admixture being univocally character-
ized by a yield shear stress (s0) and the plastic viscosity (gp) val-
ues. The reported data clearly showed that for all the
investigated formulations, the presence of these nG platelets
induced a thickening of the cementitious admixture, all the s0
and gp values being higher with respect to those registered for
the control sample. According to our previous studies, the obtained
results are in very good agreement with those recorded for fresh
mortar admixtures loaded with the same amounts of graphite
nanoplatelets (GNPs). On the other side, the rehological behavior
is distinctly different, especially at highest dosages, from that
observed for graphene oxide (GO) [29]. According to the Literature
[1,36–38], the reduced workability of fresh GBMs-modified cemen-
titious admixtures has to be associated to the shortage of available
free water, due to the presence of the high specific surface area
nanofiller. Thus, the increased friction in the body of the admixture
finally induced the observed smooth decreased workability
[49,50]. As reported in the following paragraph, such drawback
was fully counterbalanced by the multiple expected strengthening
6 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687

Fig. 5. (a) Raman spectrum (courtesy of Nanesa), (b) X-Ray diffraction pattern and (c) Scanning electron microscopy (SEM) of nano-Graphite (nG).

Table 1 control and, in some cases, it was even higher than that obtained
Purity, size, thickness, specific surface area (SSA) and composition of commercial for the control at 200 days; at 28 days, all the samples showed
nano-Graphite (nG) dry powder (courtesy of Asbury Carbons).
around 15% increased density. Interestingly, the trend for nG-0.1
Carbon content Average lateral size Thickness SSA and nG-0.2 was comparable, showing a slight increase mainly
(wt%) (nm) (nm) (m2/g) between 7 and 14 days that is further maintained at 28 days
97.5 100 6–7 402 [51]. It is worthy to notice that samples containing the lowest
amount of nanofiller (i.e. 0.01% wt) showed the highest density
effects associated to the presence of the nano-Graphite dispersed at both 7 and 14 days, that finally is slightly reduced at 28 days.
within the cement matrix. According to several authors, the observed density enhancement
Regarding the apparent viscosity (Fig. 2b), in agreement with has to be mainly attributed to the action of the GBMs as pore
the Literature and with our previous studies, the fresh admixtures refinement agent [23,52,53]. It is worthy to mention that the den-
showed a typical downward trend from low to high shear rate sity of the control sample reduced from 14 to 28 days and then
range [35]. increased at 200 days. This has to be explained considering that
the mass and the volume of cementitious samples decrease over
the hydration time. At 14 to 28 days, the effect due to the mass
3.3. Density, mechanical properties and microstructure of nG-modified reduction dominated over the volume reduction of the samples;
hardened mortars at 200 days, the reverse phenomenon occurred and density
increased [54,55].
The evolution of density at 7, 14 or 28 days for samples loaded Results of compressive strength (Rc) and flexural strength (Rb)
with different amounts of nano-Graphite (i.e. 0.01, 0.1 or 0.2% by are reported in Fig. 7b–c, respectively. Regarding Rc, all the hard-
weight of cement) is reported in Fig. 7a. The presence of the nano- ened nano-Graphite modified mortars showed a strengthening
filler clearly induced a density enhancement with respect to the effect with respect to the control sample. At 28 days, the compres-

Table 2
Rheological properties of the fresh admixtures obtained by adding different amounts of nano-Graphite to the premixed mortar.

Sample Fitting Equation s ¼ s0 þ gp  c þ c  c2 s0 (Pa) gp (Pa.s) Correlation coefficient (R2)

CS y = 0.0012x2 + 0.1745x + 16.599 16.599 0.1745 R2 = 0.9987

nG-0.01 y = -0.0001x2 + 0.285x + 23.026 23.026 0.285 R2 = 0.9907
nG-0.1 y = 0.0004x2 + 0.279x + 20.761 20.761 0.279 R2 = 0.9996
nG-0.2 y = -8E-05x2 + 0.3167x + 22.78 22.78 0.3167 R2 = 0.9975
 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687 7

Fig. 6. Rheological behavior of the fresh admixtures obtained by adding different amounts of nano-Graphite to the premixed mortar (a) shear rate (c) versus shear stress (s)
and (b) shear rate (c) versus apparent viscosity (g).

Fig. 7. (a) Density, (b) compressive strength (Rc), and (c) flexural strength (Rb) of mortars modified with different amounts of nG @ 7, 14, and 28 days.

sive strength increased by 18%, 25% and 30%, reaching, respec- For all the investigated cement-based nanocomposites, the flex-
tively, 5.7 MPa, 6.0 MPa, and 6.2 MPa for nG-0.01, nG-0.1 and ural strength (Rb) increased progressively with time following a
nG-0.2 (i.e. Rc was 4.8 MPa for the control sample). comparable trend. At 28 days, the Rb enhancement was, as an aver-
8 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
age for the three different formulations, around 20%. Interestingly,
the compressive and flexural strength of the lowest dosage of
nano-Graphite at 14 and 28 days reached, or even exceeded, the
values reported for the control sample at 200 days (Fig. 7b-c).
According to several Authors, the significant increase in both
flexural and compressive strength has to be attributed to the
ultra-strong interfacial chemical bonding between the nanofiller
and the cementitious matrix, such effect is combined and amplified
by the improved densification due to the pore refinement. In this
respect, see also the herein results reported in the following para-
graph [56–58].
SEM micrographs of nG-modified mortars and control sample
hardened at 28 days are reported in Fig. 8a–d. The typical honey-
comb morphology of C–S–H hydrated products, the characteristic
portlandite polygonal crystals and ettringite needles are clearly
visible. At the microscale level, the presence of nG seems not to
induce observable microstructural effects. However, in order to
further investigate the microstructural features of nG-modified
mortars, the volume of permeable voids has been estimated as
herein reported in the following paragraph.
3.4. Permeability of hardened composites
It is well known that the durability of cementitious materials is
directly related to their transport properties [59,60]. However, pre-
sently, the durability of GBMs-modified cement-based materials
has been rarely investigated.
Several methods have been proposed to predict the water
intake of these materials, including initial surface absorption,
water contact angle and saturation methods.
3.4.1. Initial surface absorption test (ISAT)
Initial Surface Absorption Test (ISAT) has been recently pro-
posed by several Authors to measure the primary absorption of
water into cementitious materials [61–64].The ISAT test measures
the capability of cementitious composites to resist the water
absorption by their porous outer surface at a certain time, as spec-
ified by the standard. As reported by Alani et al., the initial surface
absorption has a direct relation with the porosity of the cement-
base materials, that higher porosity is expected to result in
increased water absorption [63].
The initial surface water absorption test was assessed after
28 days of curing, results are illustrated in Fig. 9. For all composi-
tions, a similar trend was observed; the flow rate gradually
decreased by increasing the test time. The water absorption of
the control sample varied between 0.62 and 0.46 ml/m2s. In the
case of nG-0.01 and nG-0.1, comparable results were obtained
and the water absorption ranged between 0.28 and 0.19 ml/m2s.
On the other side, sample nG-0.2, containing the highest amount
of nanofiller, showed the lowest water absorption that ranged
between 0.17 and 0.12 ml/m2s. According to earlier studies
[49,65], and also in line with previously herein discussed results,
the incorporation of GBMs in cement-based materials led to
microstructural refinement that result in enhanced densification
and associated reduced water absorption. Moreover, the presence
of GBMs as nanofiller is expected not only to act as a physical bar-
rier but also to induce the formation of tortuous network paths
that finally result in decreased water penetration [66]. For
instance, Du et al. reported that the addition of 5% GNPs reduced
the average water absorption by 75%. Some Authors suggested also
that the layered structure of GNPs is more effective as a barrier
compared to spherically-shaped nanofillers, such as nano-SiO2
and nano-TiO2 [67,68].
3.4.2. Water contact angle
The water intake phenomena might be diminished incorporat-
ing suitable additives to reduce the hydrophilicity of the cementi-
tious materials [37], as it can be directly assessed by means of
water contact angle test. For example, Ranjbar et al. studied such
phenomena on geopolymers loaded with 0%, 0.1%, 0.5% and 1%
GNPs and reported the considerable reduction in the wettability
(increasing the contact angle) of geopolymers by increasing the
GNPs dosage [36].
Cementitious materials are generally at the risk of deterioration
due to the penetration of aggressive compounds that might
remarkably affect the durability of the cementitious structures
[69]. Therefore, the presence of hydrophobic nanofillers might pro-
tect the material from water penetration. As shown in Fig. 10 a–d,
the water contact angle gradually increased from 12.6° for control
sample to 24.5°, 56.3° and 78.4° for nG-0.01, nG-0.1 and nG-0.2,
respectively. These considerable increase in water contact angles
could be associated to the presence of hydrophobic
nano-Graphite platelets and/or to pore refinement, as previously
discussed in this paper concerning the ISAT test. Generally, the
presence of hydrophobic fillers in cementitious materials inhibits
the water uptake through the capillary voids by weakening the
bonds between the cementitious matrix and the water molecules
[70]. On the other hand, as reported by Gray et al., the porosity
has an inverse relation with capillary pressure meaning that the
pore refinement leads to increase the capillary pressure and water
contact angle [71].
3.4.3. Volume of permeable voids (VPV)
In porous materials the voids are generally distinguished in
open or closed porosity. In cement-base materials, the open voids
are further sub-divided into permeable, very narrow, and dead-
end pores. The volume of permeable voids (VPV) is defined as
the volume of capillary voids in mortars or concrete [72]. Thus,
the VPV term does not mainly express the total porosity [34] but
approximately predicts the overall water permeability of cementi-
tious materials [73].
Moreover, permeable voids can accommodate water that might
cause fractures below freezing temperatures, leading to decreased
durability and mechanical strength of cement-based construction
materials [56,57].
The present investigation showed that the volume of permeable
voids decreased from around 29% for the control sample to, respec-
tively, 27% and down to 25% for nG-0.01 (and nG-0.1) and nG-0.2.
In good agreement with several Authors, these results support the
previously hypothesized pore refinement effect induced by the
nanofiller, eventually combined with the formation of tortuous
barrier network that finally leads to decreased water penetration
[44,58,59].
3.4.4. Salt ponding test
Chloride ion diffusion is considered as one of the most impor-
tant term that can severely compromise the durability of
cement-based construction materials due to the increased corro-
sion rate of reinforcing steel bars associated to the penetration of
chloride ions within the cement matrix. In this respect,
graphene-based cement nanocomposites could be potentially very
interesting due to their potentiality to reduce the chloride ion dif-
fusion mainly associated to improved hydrophobicity, accelerated
hydration kinetics and enhanced densification [74]. Very recently,
several papers focused on the effect of GBMs in mortars or concrete
toward the diffusion of chloride ions [75,76]. For example, Du et al.
showed that the addition of 1.5% by weight of cement of such
nanofiller induced in concrete a decreased chloride depth by 60–
70% [18].
 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687 9

Fig. 8. Scanning electron microscopy (SEM) micrographs of (a) control sample, (b) nG-0.01, (c) nG-0.1 and (d) nG-0.2 samples @ 28 days.

Fig. 11 shows the chloride content at different depths (i.e. 5, 10, also affected transport properties. They reported that concrete
15, 20, and 25 mm) after ponding hardened samples in the NaCl modified with 1.5% (by weight of cement) of nano-Graphite
water solution. As expected, all the samples showed that the chlo- showed decreased water permeability, chloride diffusion coeffi-
ride content diminished with depth. Moreover, interestingly, a pro- cient and chloride migration coefficient by 80%, 80% and 37%,
gressive decrement of the chloride penetration was clearly respectively [17].
observed in samples loaded with increased amount of nanofiller.
Such enhancement in the transport properties has to be associ-
3.5. Physical properties of hardened nanocomposites
ated to the typical layered structure of nano-Graphite, the chloride
ions remaining ‘‘entrapped” in between the numerous graphene
3.5.1. Damping ratio
layers that built up each nanoplatelets. The same effect has been
The ‘‘damping ratio” has been introduced as a quantitative
reported by several other Authors [11,74,77]. For example, Du
parameter to indicate the ability of a certain material to mitigate
et al. reported that, besides the development of a barrier network
vibration energy and resonance., for most concrete buildings, the
enhanced densification and pore refinement, the presence of GNPs
value of the damping ratio ranges between 1% and 3% [32,33]. In
10 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
Fig. 9. Initial Surface Absorption tests (ISAT) performed on mortars modified with
different amounts of nano-Graphite @ 28 days.
order to improve the damping properties of cementitious materi-
als, several approaches have been pursed mainly based on the
addition of various fillers such as polymeric fibers, carbon fibers,
and rubber tire crumbs [78]. Regarding carbon-based nanomateri-
als, it has been assessed that multi-wall carbon nanotubes
(MWNTs) increased the damping ratio of a cement paste approxi-
mately by 20% [66,67].
Results of damping test performed on nG-modified mortars are
resumed in Table 3. Interestingly, mortars containing the lowest
dosage of nano-graphite (i.e. nG-0.01) showed the highest effec-
tiveness, the damping ratio improving by 68%;the addition of
higher amounts of nanofiller resulted in nanocomposites (i.e. nG-
0.1 and nG-0.2) characterized by a much lower damping ratio
Fig. 10. Water contact angle of (a) control sample (b) nG-0.01, (c) nG-0.1 and (d) nG-0.2 samples @ 28 days.
enhancement (i.e. 16–20%). Most probably, once more, such result
has to be associated to the higher homogeneity of samples loaded
with the lowest amount of nG due to the lower tendency of the
nanofiller to form large aggregates [79]. The observed damping
ratio enhancement of graphene reinforced cementitious materials
mainly relays on two mechanisms. First, the self-interlayer disloca-
tion slip caused by the weak delocalized pbonds and van der Waals
forces among the graphene layers which are thus allowed to easily
slip and absorb the vibration energy. Second, since the vibration
energy converts to the heat energy generated by the interfacial
friction between the nanofiller and the components of hydrated
cement matrix, the superior thermal conductivity of nG-modified
composites (see following paragraph) leads to dissipate more heat
energy, thus resulting in nanocomposites of increased damping
ratio.
These results are fully aligned with the results previously
obtained by other Authors. For instance, Ruan et al. improved the
damping ratio of cementitious nanocomposite by 16% and 45% by
introducing, respectively, 1% and 5% (by weight of cement) of
multi-layer graphene (MLGs) [79]; Long et al. performed the
dynamic mechanical testing of graphene oxide (GO) reinforced
cement paste and reported that the addition of 0.05%, 0.1% and
0.2% (by weight of cement) of GO resulted in increased loss factor
(i.e. energy dissipation capacity), respectively, by 31%, 58% and
77% combined with an increased storage modulus up to 52% for
samples containing 0.1% graphene oxide. For higher graphene
oxide contents, the poor dispersion of the nanofiller within the
cement matrix induced a remarkable decrease in the storage mod-
ulus [80].
3.5.2. Electrical resistivity
Several methods have been proposed to measure the electrical
conductivity of cementitious composites [40,81]. The Electrochem-
ical Impedance Spectroscopy (EIS), considered preferable since it
can be carried out directly in-site [71,72], has been widely applied
 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
Fig. 11. Chloride ion diffusion at different depths of nano-Graphite modified
mortars @28 days.
Table 3
Damping ratio of hardened nanocomposite mortars modified with different amounts
of nano-Graphite (nG) versus the control sample (CS) @ 28 days
Samples Average
CS 2.26 (±0.37)
nG-0.01 3.81(±0.29)
nG-0.1 2.71 (±0.43)
nG-0.2 2.62(±0.34)
to evaluate the electrical conductivity of cement-based nanocom-
posites [82].
In this study, the resistivity of nG-modified mortars was mea-
sured at 7, 14, and 28 days (Fig. 12). It resulted that the resistivity
of the control sample gradually increased with curing time. On the
other side, the resistivity of the nanocomposites was almost con-
stant at early ages and increased, but remained lower with respect
to the control, only for samples hardened for 28 days. These results
are in good agreement with several other studies [11,27,83]. For
example, Li et al. demonstrated that the presence of graphene oxide
nanostructures provide an electrically conductive pathways that
led to hardened mortars of improved electrical conductivity
[41,81]. Significant decrease in the resistivity of cement-based
nanocomposites modified with small amounts of GNPs has been
also reported [11,83].
According to the results reported in Fig. 12, mortars loaded with
0.01%wt of nG showed the best performance, the resistivity being
reduced by about 30%. Reasonably, it might be thus assumed that
Fig. 12. Electrical resistivity of mortars loaded with different amounts of nG @ 7, 14
and 28 days.
11
0.01-nG samples are characterized by an optimized dispersion of
the nanofiller through the cement matrix that finally resulted in
privileged free conductive pathways [12]. In this respect, it is wor-
thy to mention that SEM can occasionally identify GBMs dispersed
within a cementitious matrix, as reported for example by Tao et al.
[84]. Regarding the herein investigated nanocomposites, SEM was
not able to detect nG platelets, nor as single particles nor as clus-
ters and/or agglomerates (Fig. 8). It can be reasonably assumed
that the high SSA nanosized platelets (Table 1) are fully coated
by hydration products, thus preventing their detection even in
the backscattered electron (BSE) mode. This would be also in line
with the information provided by the nG supplier regarding the
proprietary process that ensures significantly reduced agglomera-
tions so that the incorporation in the final product is allowed with
the minimum applied shear [85]. Moreover, to further support this
hypothesis, Krystek et al. gave recently a robust evidence that the
enhancement of the mechanical and physical properties in nG-
modified mortars has to be associated with the achievement of
an effective nanofiller dispersion [86].
3.5.3. Thermal conductivity
Increase (%)
It has been demonstrated that the production of conductive
– pathways due to the presence of GBMs, characterized by high ther-
68
mal conductivity (i.e.3.0–5.3  103 W/mK), might potentially
20
16
improve the thermal conductivity of the resulting cement-based
nanocomposites [11].On the other hand, owing to the exothermal
nature of the cement hydration process, incorporation of GBMs
can pass the excess heat and prevent the production of early-age
cracking [87,88].
The thermal conductivity of mortars loaded with different
dosage of nG was tested, results are pictured in Fig. 13. For all sam-
ples, a considerable improvement of thermal conductivity was
recorded, the thermal conductivity increasing from 0.86 W/mK
for the control sample to 1.33 W/mK for nG-0.01, and around
1 W/mK for both nG-0.1 and nG-0.2. Once more, the highest
improvement (i.e. 55%) was obtained for mortars loaded with the
lowest nG dosage (i.e. 0.01% by weight of cement). Also in this case,
the results are in good agreement with the Literature [87]. For
example, Cui et al. reported the 70% increase in thermal conductiv-
ity by addition of 5 vol% GNPs in cementitious nanocomposites
[46]. These studies suggest that the thermal properties of these
materials depend not only on the porosity of the nanocomposites
but they are also are strictly related to the dispersion of the nano-
filler within the cement matrix. On this basis, regarding the 0.01-
nG sample, it can be reasonably assumed that a lower agglomera-
tion degree occurred thus enabling, combined with porosity reduc-
Fig. 13. Thermal conductivity of mortars loaded with different amounts of nG @
28 days.
12 M. Chougan et al. / Construction and Building Materials 259 (2020) 119687
tion (see previously paragraph), higher conductive pathways that
facilitate heat transfer and electron mobility. Finally, it is worthy
to notice that these results are also in line with those previously
discussed regarding the electrical resistivity. Such effect can be
attributed to the phonon transfer modification inside the
nanocomposite generated by the stable crystal structure and
ordered carbon atom layers of nG platelets [89].
Concluding, the lowest dosage of nano-Graphite (i.e. 0.01% by
weight of cement) clearly leads to cementitious nanocomposites
characterized by the highest enhancement in damping ratio, elec-
trical and thermal conductivity. On the basis of the Literature, it
has been hypothesized that such phenomenon has to be related
to a minimized agglomeration that results in an optimized nanofil-
ler dispersion within the cementitious matrix, finally leading to a
lowered percolation threshold [84,90,91].
4. Conclusions
The main objective of this original study was to figure out the
effectiveness of the different dosages of nano-Grafite (nG) (i.e.
0.01, 0.1, 0.2% by weight of cement) on the rheology, microstruc-
ture, mechanical and physical properties of a commercial premixed
mortar at both early (7 and 14 days) and later ages (28 days). It has
been herein clearly demonstrated that the presence of nG platelets,
even and mostly in the lowest considered amount, induced a
remarkable positive effect on the overall performance of the result-
ing cement-based nanocomposites. The main concluding remarks
have been drawn out in the following points:
(a) smooth loss of workability, the flow-ability of the fresh
admixtures decreasing with increasing the nano-Graphite
dosage;
(b) density enhancement (up to 15%);
(c) improved mechanical properties, increasing trend with the
nano-Graphite dosage (up to 30% and 20%, for compressive
and bending strength, respectively);
(d) decreased permeability with increasing the nano-Graphite
content (up to 12% decrease in volume of permeable voids);
(e) enhanced physical properties up to 68%, 30% and 55% for,
respectively, damping ratio, electrical and thermal conduc-
tivity, in the case of mortars loaded with 0.01% of nano-
Graphite by weight of cement the employ of the minimum
amount of nanofiller being able to effectively reduce the
overall drawbacks associated to the strong agglomeration
tendency typical of GBMs.
On this basis, it can be finally concluded that nano-graphite
modified cement-based materials has to be considered high-
performance and valuable multifunctional nanocomposites suit-
able for several emerging applications in the field of civil
engineering.
CRediT authorship contribution statement
Mehdi Chougan: Investigation, Data curation, Visualization,
Formal analysis, Writing - original draft, Writing - review & editing.
Emanuele Marotta: Methodology, Investigation, Writing - original
draft. Francesca R. Lamastra: Investigation, Writing - original
draft. Francesco Vivio: Resources, Methodology. Giampiero Mon-
tesperelli: Methodology. Ugo Ianniruberto: Resources, Methodol-
ogy. Seyed Hamidreza Ghaffar: Resources, Methodology, Writing -
original draft. Mazen J. Al-kheetan: Investigation. Alessandra
Bianco: Conceptualization, Resources, Supervision, Writing - orig-
inal draft, Writing - review & editing.
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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