Journal of Building Engineering 27 (2020) 101007

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Journal of Building Engineering

journal homepage: http://www.elsevier.com/locate/jobe

Effect of graphene oxide on mechanical and durability performance

of concrete
S.C. Devi a, *, R.A. Khan b
a
Deptt. of Civil Engg, Dr. B. R. Ambedkar NIT Jalandhar, Punjab, 144011, India
b
Deptt. of Civil Engg, Z. H. College of Engg. & Tech, AMU, Aligarh, Uttar Pradesh, 202002, India

A R T I C L E I N F O A B S T R A C T

Keywords: Graphene oxide (GO) may have a huge impact in construction industry in near future. Because of the oxygenated
Graphene oxide functionalities attached on the aromatic structure, it has better dispersibility property than any other graphene-
Mechanical properties based derived. Many of the researchers have given their views on the influence of GO on the mechanical and
Water permeation
durability properties in ceramic matrix. Five mixes were prepared with inclusion of GO (0%, 0.02%, 0.04%,
Hydrates of cement
Nano-reinforced concrete composites
0.06% and 0.08% by weight of cement). Tests on mechanical and water permeation properties were conducted.
The compressive and tensile strength of the mix with 0.08% GO has shown a better result compared to rest of the
mixes. The sorptivity and permeability of the nano-reinforced concrete mixes in addition of GO were observed to
have reduced with increasing GO content in the concrete compared to the control mix. The synthesized GO was
structurally characterized by means of FE-SEM/EDX, FT-IR and XRD. Microstructural analysis was carried out
using SEM/EDX on 90 days old concrete mixes and the quality of the concrete mixes was checked with UPV test.

1. Introduction composites [2,3].

Cement is the basic binding material used in concrete with the major
drawback of being brittle with low tensile strength. With due course of
time these drawbacks were taken care with the introduction of steel
reinforcement and fibers. But the introduction of nanomaterials in
cement-based composites have enhanced the properties such as tough­
ness, flexural, tensile and durability properties by improving at the
nanoscale of the concrete. Nanotechnology has proved that composites
can be modified/re-engineered with a small inclusion of nano-materials
[1]. Carbon Nano-Tubes (CNTs), graphene-derived, Carbon nanofibers
(CNFs), nanosilica, etc. are very popular among all the nanomaterials.
Nanocomposites has proven its ability to enhance the properties of the
parental material. Nanomaterials in concrete industry have become a
trend as it has many advantages from enhancement in mechanical
strength to filling the voids at nano-level. The chemistry of cement and
nanomaterials such as CNTs, graphene, graphene oxide (GO),
graphene-based nanomaterials are observed to have improved the me­
chanical, thermal, electrical, optical etc. properties of the cement com­
posites. Many of the researchers have worked on the mechanical and
durability properties on nano-reinforced cement composites. And as
usual it has shown better results than the conventional cement
Graphene oxide is also a carbon-based nanomaterial. Graphene oxide
was first-hand prepared by Benjamin C. Brodie [4] in 1859 by chemical
exfoliating graphite (further modified by Hummer). Like graphite, gra­
phene oxide has aromatic structure like any other graphene
based-derived, but due to the chemical reactions occurred, some of the
covalent bonds were broken down and functional groups such as epoxy,
carbonyl, hydroxyl, phenol etc. were attached on the sp2 aromatic
monolayer structure (about one atom-thick) [5,6]. The functionalities
have its perk when introduced to cement-based composites. These
oxygenated functionalities are hydrophilic in nature and easily adsorbs
free radicles of water from the cement composite prepared. Graphene
oxide has large specific surface area with higher aspect ratios. Generally,
nanomaterials have one big disadvantage with their dispersibility
property but in case of GO, it has dominance over any other nano­
materials because of the oxidative functionalities which allow to
disperse easily in water. Chuah et al. have mention that the degree of
sonication was independent for GO dispersion in water but tend to
reagglomerate as the abhorent forces provided by oxygenated functional
groups at GO sheets was overpowered by van der Waals forces between
the GO nanosheets [7]. However, a compatible surfactant (poly­
carboxylate ether-based) stabilized the GO dispersion in cement-based

* Corresponding author.
E-mail address: sanglakpamc@gmail.com (S.C. Devi).

https://doi.org/10.1016/j.jobe.2019.101007
Received 27 November 2018; Received in revised form 16 October 2019; Accepted 17 October 2019
Available online 20 October 2019
2352-7102/© 2019 Elsevier Ltd. All rights reserved.
S.C. Devi and R.A. Khan
composites.
Addition of GO in cement-based composites have an adverse effect
on the workability due to its large surface area that tend to absorb more
water molecule to get wet and a bulky lateral size with high capacity for
water retention created due to cluster of GO nanosheets [8,9]. Regard­
less of the above mention disadvantage of GO, incorporation of small
content of GO of about 1% by weight of cement (bwoc) have improved
the compressive strength by 63% [10]. The addition of 0.05% GO
(bwoc) was reported to enhanced the compressive strength by 15–33%
and flexural strength by 41–58% [3,11]. Shang et al. have stated that the
compressive strength with 0.04% GO inclusion to the cement paste was
improved up to 15.1% compared to plain cement paste [12]. The
compressive strength and tensile strength were increased by over 40%
with 0.03% GO inclusion by weight of cement (bwoc) to OPC paste at 28
days curing age [13]. Mohammed et al. concluded that the addition of
GO led to enhancement of water sorptivity and chloride penetration
values whereas it reduces the pore size of the GO reinforced cement
paste indicating the improvement of resistance to chemical ingress [14].
Some researchers have quoted that GO inclusion accelerated the heat of
hydration. The GO sheets with oxygenated functionalities make more
approachable to the cement particles, thus allowing the nanosheets to
act as nuclei for the cement phases boosting the reaction of cement with
water [14]. Wang et al. have mentioned that the microstructure of the
GO reinforced cement matrix have massive crystal structure covering
implying leaching of calcium hydroxide (CH) during the hydration
stages have been improved at 28 days curing age [15].
The GO inclusion cement matrix is in trend due to its exceptional
properties. Interest in GO has grown worldwide in various fields as GO is
way cheaper compared to extremely expensive multi-walled CNTs,
single-walled CNTs and CNFs (which is 250, 1280 and 218 times more
than price of GO per 100g) [16]. Thus, GO became the best candidate for
this investigation. This investigaton was carried out to develop a
nano-reinforced concrete composite in addition of GO with varying
percentage by weight of cement. No study has been reported on GO
inclusion in concrete (with natural coarse and fine aggregate) compos­
ites with regards to workability, compressive strength, tensile strength,
water permeation, sorptivity, quality of the nano-reinforced concrete
composites and the cost analysis to get a clear picture whether this
investigation will be helpful for practical application in construction
industry.
2. Experimental program
2.1. Materials
Raw GO was synthesized using modified Hummer’s method [17,18],
graphite powder (10g) and sodium nitrate, NaNO3 (5g) were allowed to
react with conc. sulfuric acid, H2SO4 (230 mL) at 20 � C temperature on
heater stirrer for over a period of 30 min and then gradually added
potassium permanganate, KMnO4 (30g). The resulting mixture were
heat up to 35 � C for another 30 min and slowly diluted with 230 ml
water. The mixtures were then heated up to 98 � C for 15 min and 3%
hydrogen peroxide (H2O2) were added to complete the reaction fol­
lowed by 400 mL deionized (DI) water and allowed to settle. And finally,
washed the dilute solution of GO with 1:10 HCl and 4 L DI water until
the pH of the filtrate was up to 7. The filtered paste was then oven dried
at 65 � C for 24 h to obtained required GO powder. The chemicals used
were procured from LOBA chemicals. And the GO obtained was then
characterized structurally using SEM/EDX, XRD and FT-IR techniques to
check the composition of the near surface, crystalline structure and to
identify the functional groups present.
OPC 43 grade, meeting the specification as per IS 8112:1989 [19],
fine aggregate used were locally available which lie in Zone II, con­
forming IS 383: 1997 [20], and natural coarse aggregate of maximum
nominal size 12.5 mm. The fineness modulus, specific gravity and bulk
modulus of fine and coarse aggregate were 2.74 and 7.54, 2.67 and 2.64,
2
Journal of Building Engineering 27 (2020) 101007
1675 kg/m3 and 1690 kg/m3 respectively. Table 1 shows the physical
properties of the OPC. And MG SKY 8765 (polycarboxylate based) super
plasticizer were procured from local dealer conforming to IS 9103:1999
[21].
2.2. Mix proportions and casting
A total of five mixes were prepared and tests were performed on both
fresh concrete and hardened concrete at different curing ages. The
binder, fine and coarse aggregate was kept constant at 384 kg/m3,
715 kg/m3 and 1113 kg/m3 respectively (1:1.86:2.89) with w/b ratio
0.45. GO were added with varying percentage content by weight of
cement from 0 to 0.08% with an increment of 0.02%. The mix pro­
portions are given in Table 2. The GO was allowed to dispersed using
500 W cup-horn high intensity ultrasonic processor [22] in an aqueous
solution containing 0.05% (bwoc) super plasticizer (used as surfactant)
kept constant for all the mixes in a sonicator with ultrasonic energy of
about 2000J/min at cycles of 20s (to avoid overheating) operated at
50% constant amplitude for 30 min. Further, the solution was stirred on
a 2000 ml capacity magnetic stirrer till the ingredients were introduces
to the mixer. The 10% and 20% of total water of the mix were used in the
exfoliation process using sonicator and magnetic stirrer respectively.
The mechanical exfoliation was carried out with different loading levels
of GO (0.02%, 0.04%, 0.06% and 0.08%).
A homogeneous mixture of cement, sand, coarse aggregate and 70%
of water was prepared in a power-driven laboratory (220–240 V power
input) mixer of 300L capacity at 22–24 rmp for 3 min. The remaining
30% water with exfoliated GO nano-sheets was added to the mixer and
rotated for another 2 min. The fresh concrete was then poured on the
oiled moulds of respective shape and sample sizes. After 24 h and water
cured for 7, 28, 56 and 90 days in a temperature (27 � 2 � C and 90%
humidity) regulated curing tank till the age of testing.
2.3. Test method
2.3.1. Slump test
Workability is the ability to be mixed, handled, transported and
placed with a minimum loss of homogeneity i.e. segregation or bleeding.
Workability of the fresh concrete was performed as per IS: 6461 (Part
VII)- 1973 [23] and the designed slump value for the control mix i.e. 0%
GO content concrete mix was 100 mm. The slump value was evaluated
using slump cone test after pouring the fresh concrete in the cone (200ɸ
mm, 100 ɸ mm and 300 mm height) in four layers (1/4 of height of the
mould) by tamping each layer 25 times and lifted and the height of
coned concrete was measured. The slump value for different mixes were
recorded and the influence of GO in the fluidity of the nano-reinforced
concrete composites.
2.3.2. Mechanical properties
As per code IS: 516–1959 [24] and IS: 5816–1999 [25], the test was
conducted on 100 mm cubes for compressive and splitting tensile
strength (diagonally splitting the cube, stress (σ) ¼ 0.5187 Load/Side2)
Table 1
Physical properties of OPC.
Characteristic Properties OPC
Specific Gravity 3.15
Specific Surface Area (m2/kg) 300
Compressive Strength (MPa)
3 Days 24.6
7 Days 34.3
28 Days 45.2
Standard Consistency (%) 32
Initial Setting Time (Minutes) 62
Final Setting Time (Minutes) 270
Loss of Ignition (%) 2.04
S.C. Devi and R.A. Khan
Table 2
Quantity of materials used in kg/m3.
Mix Description OPC GO (g)
M1 OPC0GO 384 0 173
M2 OPC0.02GO 384 76.8
M3 OPC0.04GO 384 153.6
M4 OPC0.06GO 384 230.4
M5 OPC0.08GO 384 307.2
� SP – (Carboxylate based) Super Plasticizer, GO – Graphene Oxide.
for each curing age 7, 28, 56 and 90 days on 200T capacity Compression
Testing Machine (CTM). The load was allowed gradually without shock
and increased at the constant rate of 3.5 N/mm2/minute until cube
failed.
2.3.3. Test for water permeation property
2.3.3.1. Initial surface absorption. The initial surface absorption test
(ISAT) were performed on 150 mm cubes, as per BS 1881: Part 208:1996
[26], this was conducted to test the rate of flow of water into concrete
surface per unit area at specified interval. The specimens were oven
dried at 105 � C until the weight was not more than 0.1%. The setup for
the test was made in such a way that a 78 mm diameter cap is clamped to
the cube surface providing an area of water contact with the surface to
be tested of not less than 5000 mm2. The water was allowed to flow
through the inlet from the reservoir of diameter 100 mm which was
fitted with tap to an outlet attached with scale. The water head was
maintained between 180 mm and 220 mm for the test. The tap was
opened and measurements taken for 1 min at interval 10 min, 30 min
and 60 min from start of the test. The rate of flow was measured in
mL/m2s. The tests were performed on 28, 56 and 90 days curing period.
2.3.3.2. Sorptivity. A 100 � 200 mm cylinder was cut into 100 � 50 mm
disc and preconditioned by oven drying at 105 � C until the difference in
weight of the specimen was not more than 0.1%. The test was performed
as per ASTM 1585–04: 2009 [27]. The circumferential area was coated
with epoxy paint and both the circumferential and top surface were
tightly sealed using polyethylene sheets to block evaporation. The
weight of the disc was measured at 0, 1, 5, 10, 30, 60 min and for every
1-h interval up to 6 h from the start for initial rate of absorption Trends
of plots of cumulative water absorption and square root of time
(mL/√S) for all concrete mixes containing graphene oxide (GO) 0%,
0.02%, 0.04%, 0.06% and 0.08%.at 28, 56 and 90 days curing periods
were evaluated.
2.3.4. Ultrasonic pulse velocity
The ultrasonic pulse velocity (UPV) was generated by an electro-
acoustical transducer, transmitted on one surface of the concrete cube
and receiving (frequency of 54 KHz) the same by a similar transducer in
contact with the surface at the other end. A thin layer of coupling gel was
applied to facilitate higher signal. The ultrasonic pulse velocity was
carried out according to IS 13311(Part 1): 1992. The principle of eval­
uating the quality of concrete comparatively higher velocity was ob­
tained on the Pundit Lab when the quality of concrete in terms of
density, homogeneity and uniformity is good. In case of poorer quality,
lower velocities are obtained. Ranges of velocities of UPV test are given
in IS 13311(Part 1): 1992 [28]. The tests were conducted at 28, 56 and
90 days curing period.
2.3.5. Microstructural observation
The samples of the GO-reinforced concrete mixes using scanning
electron miroscopy-energy dispersive X-ray spectroscopy, SEM EDX on
JEOL JSM-6510LV. The samples were made conductive by gold coating
prior to microscopy analysis by sputtering method. To examine the
samples at 90 days of curing, the secondary electron detector was used at
Journal of Building Engineering 27 (2020) 101007
Water Fine Aggregate Coarse Aggregate SP (mL)
715 1113 192
173 715 1113 192
173 715 1113 192
173 715 1113 192
173 715 1113 192
high vacuum at an accelerating voltage of 15 KV with working distance
of 13 mm.
3. Result and discussion
3.1. Structural characterization of synthesized GO
The structural characterization of synthesized GO (powdered) was
carried out using field emission scanning electron microscopy (FE-SEM)
and energy dispersive x-ray spectroscopy (EDX) on BRUKER QUANTA
FEG 450 to obtained the element composition and surface morphology.
Fig. 1(a) and (b) the scanning electron microscopy images and the EDX
analysis of synthesized GO showing wrinkled surface with elemental
composition of near surface, the percentage of carbon content (C) and
oxygen (O) was observed to be high which indicates the attachment of
oxidative functional groups as shown in Table 3. The large surface area
of GO nanosheets interlaced with weak van der Waals bond which under
the microscopy appears to be crinkly.
The X-ray diffraction pattern for GO powder was obtained using
PANalytical EMPYREAN diffractometer with Cu Kα ¼ 1.54060 Å, scan­
ned at angular range of 2θ ¼ 5� –100� with fixed divergence slit of
0.2177� of step size of 0.0080 and step time of 12.0650 s, operated at
40 mA and 45 kV to distinguishes the interplanar spacing and the crys­
talline nature. The XRD spectra of the GO is shown in Fig. 1(c)
appearance of diffraction peak at 2θ ¼ 10.8� indicating an interlayer
spacing of 0.814 nm, which is assigned to (001) diffraction peak of
graphitic oxide. Fourier transmission infrared (FT-IR) spectra spots the
presence of functional groups of GO. This is due to the disruption of
oxygen containing functional groups on the sp2 hybridization. The FT-IR
spectra in Fig. 1(d), alkenic bonds (-C– – C- stretch) was observed at
1619 cm 1, Hydroxyl (-OH) and carbonyl groups (C– – O) were seen at
1 1
peaks 3218 cm and 1711 cm . and at 870 cm-1 peak confirms C–O
stretch in epoxides with further support by absorption peak at 1032 cm-
1, thus confirming the presence of oxidative functionalities on the GO
nanosheets.
3.2. Workability
The mix, M5 with 0.08% was observed to have significantly lower
slump tailed by M4 (0.06% GO), M3 (0.04% GO) and M2 (0.02%)
compared to the control mix M1 with 0% GO. Fig. 2 shows the com­
parison of the GO reinforced concrete composites with the parent
designed mix. The slump value of the nano-reinforced concrete com­
posites reduces with increase in percentage GO content. Thus, incor­
poration of GO in the concrete mixes reduces the workability.
Comparable results were reported on reduction of fluidity and increase
in viscosity with increase in GO content [7,29]. The high specific surface
area of GO (theoretical value of 2620 m2/g) adsorbs water from fresh
mix to wet the GO nano-sheets [9]. Also, the hydrophilic oxygenated
functionalities attached on the GO nanosheets absorbs the water mole­
cule and remains entrapped due to flocculation and agglomeration for­
mation caused by electrostatic interaction between GO and cement
particles [12,13]. Hence, with increases in GO content in the mixes the
slump value of the mixes decreases linearly.
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S.C. Devi and R.A. Khan Journal of Building Engineering 27 (2020) 101007

Fig. 1. (a) FE-SEM, (b) EDX, (c) XRD and (d) FT-IR of GO nanosheets.

have minimum increase in compressive strength of 26%. Previous

Table 3
studies have mentioned that inclusion of small portion of GO nanosheets
Chemical composition for GO.
in cement-based composites has improved the compressive strength at
Element Weight % large scale [3,12,13,30–32].
O 47.62 Lin et al. (2016) confirmed that GO acts as catalyst and helped
C 45.34 accelerating cement hydration without causing any changes in the
S 4.86 oxygenated functional groups attached in GO nanosheets [33]. These
N 1.95
Mn 0.23
functional groups act as active sites that attracts cement particles. The
high surface area to mass ratio of GO nanosheets assists the nucleation
Total 100
for formation of cement hydrates and develops strong covalent bonds at
the interface of cement matrix and dispersed phase (i.e. GO). Thus, in­
3.3. Mechanical properties clusion of GO reinforced the concrete composites at nano-level which
results in enhancement of the compressive strength of GO
3.3.1. Compressive strength nano-reinforced concrete composite compared to control mix.
The compressive and splitting tensile tests were conducted on a
compression testing machine at 7, 28, 56 and 90 days curing period. The 3.3.2. Tensile strength
mixes with GO have better compressive as well as tensile strength than Fig. 4(a) and (b) illustrates the impact of GO on the tensile strength of
the control mix, M1. The mix with 0.08% GO, M5 have the maximum nano-reinforced concrete composites. It can be observed that the mix
improvement followed by M4 (0.06% GO), M3 (0.04% GO), and M2 with 0.08% GO content shows maximum improvement of 38% and the
(0.02% GO). Fig. 3(a) and (b) represents the comparison in compressive minimum of 5% for mix containing 0.02% GO by weight of cement, in
strength and percentage increase in compressive strength of the mixes at tensile strength at 90 days curing. Various investigations on effect of GO
different curing ages. It can be observed the gradual increase in strength inclusion in cement-based composites have concluded that GO accel­
with increase in concentration of GO in the concrete mixes at different erate hydration, improve tensile and flexural strength, refining the
hydration time. The mix with 0.08% GO exhibits the maximum mechanical interlocking at the GO reinforced cement matrix interface
compressive strength after 90 days curing with 49% improvement [13,29,31,34]. Densification of microstructure may have been caused
compared to control mix. And the mix with 0.02% GO was observed to due to the high aspect ratio and filler effect of GO at nano-scale resulting

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S.C. Devi and R.A. Khan Journal of Building Engineering 27 (2020) 101007

Fig. 2. Comparison of slump value of different mixes.

Fig. 3. (a) Compressive strength for all mixes, (b) percentage increase in compressive strength (%) at different curing age of 7, 28, 56 and 90 days.

an improved mechanical strength.
Table 4 represents the reinforcing effect of GO in the compressive
strength of concrete composites of the current investigation compared to
the previous studies on GO incorporation in cement-based composites. It
was observed that inclusion of 0.03% and 0.05% GO in cement paste has
improved the strength by 40–67% and 15–33% respectively, at different
curing ages. However, inclusion of GO in mortar with varying concen­
tration ranging from 0.01% to 0.05%, 0.1%–0.125% up to 1% have been
recorded to enhanced the compressive strength by 12.2–59%, 28–56%
and 63–86% respectively, at different curing age. Similarly, in the cur­
rent study, inclusion of 0.02%–0.08% with an increment of 0.02% of GO
in concrete have improved the compressive strength by 21–55% which

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S.C. Devi and R.A. Khan Journal of Building Engineering 27 (2020) 101007

Fig. 4. (a) Splitting tensile strength for all mixes (b) percentage increase in tensile strength (%) at different curing age of 7, 28, 56 and 90 days.

cured specimens. The minimum and maximum absorption rate was

Table 4
observed to be achieved by mix prepared with 0.02% and 0.08% GO
Comparison of compressive strength in cement-based nanocomposites rein­
addition in concrete composite which was observed to have reduced the
forced with GO.
absorption rate with reference to control mix by 6.5% and 34%
Matrix GO concentration w/c % increase in compressive Source respectively, at 90 days curing age. A gradual reduction in surface ab­
% (bwoc) strength at different curing
age
sorption of the nano-reinforced concrete mixes was clearly observed for
28 and 56 days curing period. Earlier investigations have reported that
Paste 0.03 0.5 40–67 [13]
GO incorporation in cement-based composites fabricates by reassem­
Paste 0.05 0.5 15–33 [3]
Mortar 0.01–0.05 0.37 12.2–59 [31] bling GO sheets due to weak van der Waals bond with the matrix [36,
Mortar 1.00 0.45 63–86 [30] 37]. Also, the nanosheets when interlocked with more GO sheets gets
Mortar 0.1–0.125 0.45 28–56 [16] deposited acting as a protective cloak which enhanced the resistance to
Concrete 0.02–0.08 0.45 21–55 Current chemical ingress. Thus, the mixes made with GO have shown lesser
study
surface absorption for both the curing age relatively to the control mix,
which may be due to the fact that GO as a filler material filled the voids
may be attributed to the strong interfacial bonding between the matrices at nano-level and not allowing further absorption of water molecule at
arising from the two-dimensional crumpled structure with high specific respective interval of time.
surface area of GO [35]. The reinforcing effect of GO on strength of
concrete makes GO a promising reinforcement in cement-based concrete 3.4.2. Sorptivity
composites. This method was used to govern the rate of absorption of water by
evaluating the increment in mass caused by the water absorption (only
one face of the sample) with respect to time. It was observed that the
3.4. Water permeation property
sorptivity (mm/s1/2) for all the mixes with GO inclusion for 28, 56 and
90 days curing as shown in Fig. 6, has lesser value than control mixed.
3.4.1. The initial surface absorption test
The percentage reduction in rate of absorption was maximum for mix
The initial surface absorption test (ISAT) was conducted on all the
prepared with 0.08% GO inclusion at 90 days curing about which was
five mixes on a 150 � 150 � 150 mm cube of 28 and 56 days curing age.
observed to be 46% and the minimum reduction was recorded to be 18%
The absorption rate was obtained by assessing the uniaxial water
of mix made with 0.02%GO compared to the control mix. Mohammed
penetration on to the surface of the concrete. The results of the test are
et al. mentioned that addition of GO influences the transport properties
shown in Fig. 5. It was recorded that the absorption was high for all the
in cement matrix which improved the gel pores and strengthened the
mixes at their 28 days of curing compared to the result of the 56 days

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S.C. Devi and R.A. Khan Journal of Building Engineering 27 (2020) 101007

Fig. 5. Initial surface absorption rate for 28, 56 and 90 days curing of the GO-reinforced concrete composites.

Fig. 6. Sorptivity of the mixes for 28, 56 and 90 days.

microstructure of the matrix [13,14]. It can be observed that with in­ cement hydrates was indeed accelerated with GO incorporation in the
crease in GO concentration level the porosity of the GO reinforced cement matrix.
concrete mixes have been reduced, i.e. the nucleation for formation of

Fig. 7. Ultrasonic Pulse Velocity for all the mixes for 28 and 56 days.

7
S.C. Devi and R.A. Khan
3.5. Ultrasonic pulse velocity
The quality of the concrete was determined by conducting UPV test
on the hardened concrete of all mixes on 28, 56 and 90 days curing
period. The homogeneity of the concrete was obtained from the fact that
the pulse velocity of transducer passes through at a high or low velocity.
Fig. 7 Represents the quality of the concrete mixes in comparison to the
control mixed. The pulse velocity less than 3 km/s means a very poor
quality, between 3 and 3.5 km/s a medium, 3.5–4.5 km/s a good one and
Fig. 8. SEM images for (a) M1 (CM), (b) M2 (0.02% GO), (c) M3 (0.04% GO), (d) M4 (0.06% GO) and (e) M5 (0.08% GO) for 90 days curing at 50 μm and 1 μm
magnification.
8
Journal of Building Engineering 27 (2020) 101007
more than 4.5 km/s means an excellent quality of concrete as catego­
rized by IS 13311.
It was observed that velocity of all the mixes at 28 days curing age
were of good quality concrete. But at 56 days curing the mix with 0.08%
GO content was recorded to have higher velocity compared to the
remaining mixes falling under excellent quality. And at 90 days curing
the velocity of mixes with GO with 0.08% was observed to be highest
followed by 0.06%, 0.04% and 0.02% GO concentration which reduced
to excellent quality concrete. Whereas the velocity of the control mix
S.C. Devi and R.A. Khan Journal of Building Engineering 27 (2020) 101007

Fig. 8. (continued).

was observed to be less than 4.5 km/s. This may be attributed to the
nanofiller effect of GO densifying the concrete at nano-level. Thus,
improving the homogeneity and quality of concrete reflecting on the
mechanical and durability characteristics of the concrete.
3.6. Microstructural analysis
SEM analysis were performed for all the mixes at 90 days curing age
at different magnification range i.e. 50 μm and 1 μm near the interfacial
transition zone (ITZ). The hydrated cement (crystals) was observed in
the SEM micrographs of 90 days cured concrete composites as shown in
Fig. 8 (a) control mix (b) 0.02% GO (c) 0.04% GO (d) 0.06% GO and (e)
0.08% GO. Densified hydrated cements with low density C–S–H in as­
sociation with C–H is visible in Fig. 8 (a) with microcracks attributed to
aggregate settlement in fresh state which led to the presence of excess
water content in the vicinity of the aggregate affecting the mechanical
behavior in negative way [38]. Fig. 8 (b) 0.02% GO content was
observed to have dense platy cement hydrates associated with pores.
However, the microstructure of concrete mix with 0.06% GO inclusion
undergoes significant improvement with densified hydrated crystals and
lesser pores compared to mix with 0.04% and 0.08% GO content which
may be attributed to C–S–H formation in conjunction with C–H platy
crystals and ettringite (fibrous and needle shape crystals) in Fig. 8 (c),
for spectrum 1 to 5 as shown in Fig. 8. The EDX analysis of mixes (a)
control mix (b) 0.02% GO (c) 0.04% GO (d) 0.06% GO and (e) 0.08%
GO incorporation at 90 days curing age is shown in Fig. 9. The Ca/Si
ration for control mix and mixes with GO 0.02%, 0.04% and 0.06% were
higher than 2 which specifies the hydrated products of the late stage of
hydration and C–S–H comprises of interlocked and interweaved foils
[39]. However, the Ca/Si ratio of mix with 0.08% GO concentration was
observed to be 0.2 which is much lesser than 1.5 indicating the rapid
formation C–S–H and C–H which resembles fibrillar materials entan­
gling to one another due to undergoing hydration of cement particles
[40]. Hence, GO inclusion (0.08%) has help the unreacted cement par­
ticle to hydrate at later age which affect the mechanical and durability
behavior in a positive manner.
4. Cost analysis
The cost of casting the mixed designed were analyzed and reported in
Table 6. The cost of different nano-reinforced concrete composites was
Table 5
Composition of element present in the mix obtained from SEM/EDX analysis.
Element Spectrum 1 Spectrum 2 Spectrum 3 Spectrum 4 Spectrum 5

(d) and (e) respectively. With varying GO concentration in the concrete OK 64.02 62.4 58.57 61.57 60.22
composites, the hydrated crystals continue to become complex-stacking Al K 2.51 2.19 1.16 2.01 10.98
Si K 9.59 4.74 5.81 7.01 23.98
one over the other, massive and thicker as observed from Fig. 8 implying
Ca K 23.88 17.11 20.84 20.72 4.82
addition of GO in concrete is a promising reinforcing agent in concrete. CK – 13.56 13.62 8.69 –
Table 5 represents the electron dispersive X-ray spectroscopy (EDX)
Total 100 100 100 100 100
analysis of the element percentage composition of the SEM micrographs

9
S.C. Devi and R.A. Khan
Fig. 9. EDX analysis for (a) Spectrum 1 (CM), (b) Spectrum 2 (0.02%GO), (c) Spectrum 3 (0.04% GO), (d) Spectrum 4 (0.06% GO) and (e) Spectrum 5 (0.08% GO)
for 90 days curing.
evaluated using the commercialized market prices of the materials. The
economy index (compressive strength/cost per m3) was observed to
have maximum value at mix M4 (with 0.06% GO inclusion) compare to
rest of the mixes. It shows that mix M4 is the optimum mix.
5. Conclusion
The current investigation can be drawn in to the conclusion that
inclusion of GO with different percentage content by weight of cement in
10
Journal of Building Engineering 27 (2020) 101007
developing a concrete, has reduced the workability and significantly
enhanced the compressive strength by (21–55%), tensile strength by
(16–38%) and initial surface absorption and sorptivity tends to decrease
with increase in GO content for 28, 56 and 90 days curing period. The
result of the non-destructive method (UPV) showed that the homoge­
neity of the GO reinforced concrete composite remain intact with the
increment in GO concentration, mix prepared with 0.08% has the
maximum average velocity for all the curing ages compared to control
mix and the remaining mixes. But from the cost analysis and the
S.C. Devi and R.A. Khan
Table 6
Cost analysis of different mixes.
Material (kg) Cost (Rs/Kg) Mix combination
M1
OPC 7.48 2872.32
FA 1.5 1072.5
CA 1 1113
GO 1200 0 92.16
SP 118 22.656
W 0.05 8.65
Total (INR) – 5089.13
Compressive Strength (MPa) – 36.45
EI (Strength/Cost) – 0.00716
Note- OPC-Ordinary Portland Cement, FA- Fine Aggregate, CA-Coarse Aggregate, GO- Graphene Oxide, SP- Super Plasticizer, W- Water, EI- Economy Index.
economic index point of view so calculated, it can be concluded that mix
with 0.06% GO incorporation is the optimum mix on the basis of the
maximum strength attained on 90 days curing age.
Acknowledgement
The authors would like to acknowledge the Minister of Human
Resource & Development (MHRD) New Delhi, India, for the financial
support provided during the investigation. We are grateful to IIC, NIT
Jalandhar, USIF, Aligarh Muslim University and CMSE, NIT Hamirpur
for providing the material characterization facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jobe.2019.101007.
References
[1] P. Balaguru, K. Chong, Nanotechnology and concrete: research opportunities, in:
Nanotechnology of Concrete: Recent Developments and Future Perspectives, 2006.
November 7, Denver, USA.
[2] S. Chuah, Z. Pan, J.G. Sanjayan, C.M. Wang, W.H. Duan, Nano Reinforced Cement
and Concrete Composites and New Perspective from Graphene Oxide, Constr.
Build. Mater. (2014), https://doi.org/10.1016/j.conbuildmat.2014.09.040.
[3] Z. Pan, L. He, L. Qiu, A.H. Korayem, G. Li, J.W. Zhu, F. Collins, D. Li, W.H. Duan,
M.C. Wang, Mechanical properties and microstructure of a graphene oxide-cement
composite, Cement Concr. Compos. (2015), https://doi.org/10.1016/j.
cemconcomp.2015.02.001.
[4] B.C. Brodie, On the atomic weight of Graphite : Brodie, B. C. : free download,
borrow, and Streaming : Internet archive, Philos. Trans. R. Soc. Lond. 149 (1859)
249–259, https://doi.org/10.1098/rstl.1859.0013.
[5] H.V. Kumar, S.J. Woltornist, D.H. Adamson, Fractionation and characterization of
graphene oxide by oxidation extent through emulsion stabilization, Carbon 98
(2016) 491–495, https://doi.org/10.1016/J.CARBON.2015.10.083.
[6] T. Tong, Z. Fan, Q. Liu, S. Wang, S. Tan, Q. Yu, Investigation of the effects of
graphene and graphene oxide nanoplatelets on the micro- and macro-properties of
cementitious materials, Constr. Build. Mater. 106 (2016) 102–114, https://doi.
org/10.1016/j.conbuildmat.2015.12.092.
[7] S. Chuah, W. Li, S.J. Chen, J.G. Sanjayan, W.H. Duan, Investigation on dispersion
of graphene oxide in cement composite using different surfactant treatments,
Constr. Build. Mater. 161 (2018) 519–527, https://doi.org/10.1016/j.
conbuildmat.2017.11.154.
[8] X. Li, Z. Lu, S. Chuah, W. Li, Y. Liu, W.H. Duan, Z. Li, Effects of graphene oxide
aggregates on hydration degree, sorptivity, and tensile splitting strength of cement
paste, Compos. Appl. Sci. Manuf. 100 (2017) 1–8, https://doi.org/10.1016/j.
compositesa.2017.05.002.
[9] D.A. Dikin, S. Stankovich, E.J. Zimney, R.D. Piner, G.H.B. Dommett,
G. Evmenenko, S.T. Nguyen, R.S. Ruoff, Preparation and characterization of
graphene oxide paper, Nature 448 (2007) 457–460, https://doi.org/10.1038/
nature06016.
[10] X. Li, A.H. Korayem, C. Li, Y. Liu, H. He, J.G. Sanjayan, W.H. Duan, Incorporation
of graphene oxide and silica fume into cement paste: a study of dispersion and
compressive strength, Constr. Build. Mater. 123 (2016) 327–335, https://doi.org/
10.1016/j.conbuildmat.2016.07.022.
[11] G.Y. Li, P.M. Wang, X. Zhao, Mechanical behavior and microstructure of cement
composites incorporating surface-treated multi-walled carbon nanotubes, Carbon
43 (2005) 1239–1245, https://doi.org/10.1016/J.CARBON.2004.12.017.
[12] Y. Shang, D. Zhang, C. Yang, Y. Liu, Y. Liu, Effect of graphene oxide on the
rheological properties of cement pastes, Constr. Build. Mater. 96 (2015) 20–28,
https://doi.org/10.1016/j.conbuildmat.2015.07.181.
11
Journal of Building Engineering 27 (2020) 101007
M2 M3 M4 M5
2872.32 2872.32 2872.32 2872.32
1072.5 1072.5 1072.5 1072.5
1113 1113 1113 1113
184.32 276.48 368.64
22.656 22.656 22.656 22.656
8.65 8.65 8.65 8.65
5181.29 5273.45 5365.61 5457.77
46.21 51.17 53.74 54.438
0.00892 0.0097 0.01002 0.00997
[13] K. Gong, Z. Pan, A.H. Korayem, L. Qiu, D. Li, F. Collins, C.M. Wang, W.H. Duan,
Reinforcing effects of graphene oxide on Portland cement paste, J. Mater. Civ. Eng.
27 (2014), A4014010, https://doi.org/10.1061/(asce)mt.1943-5533.0001125.
[14] A. Mohammed, J.G. Sanjayan, W.H. Duan, A. Nazari, Incorporating graphene oxide
in cement composites: a study of transport properties, Constr. Build. Mater. 84
(2015) 341–347, https://doi.org/10.1016/j.conbuildmat.2015.01.083.
[15] Q. Wang, J. Wang, C.-X. Lu, B.-W. Liu, K. Zhang, C.-Z. Li, NEW CARBON
MATERIALS Influence of graphene oxide additions on the microstructure and
mechanical strength of cement, N. Carbon Mater. 30 (2015) 349–356, https://doi.
org/10.1016/S1872-5805(15)60194-9.
[16] S. Sharma, N.C. Kothiyal, Comparative effects of pristine and ball-milled graphene
oxide on physico-chemical characteristics of cement mortar nanocomposites,
Constr. Build. Mater. 115 (2016) 256–268, https://doi.org/10.1016/j.
conbuildmat.2016.04.019.
[17] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc. 80
(1958), https://doi.org/10.1021/ja01539a017, 1339–1339.
[18] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L.
B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, ACS Nano 4
(2010) 4806–4814, https://doi.org/10.1021/nn1006368.
[19] IS 8112, 43 Grade Ordinary Portland Cement- Specification, Indian Standard.,
1990, p. 17.
[20] IS 383, Indian Standard: Coarse and Fine Aggregaes from Natural Sources for
Concrete, 1997, pp. 1–21.
[21] IS 9103, IS 9103 (1999), Specification for Concrete Admixtures, 1999.
[22] M.S. Konsta-Gdoutos, Z.S. Metaxa, S.P. Shah, Highly dispersed carbon nanotube
reinforced cement based materials, Cement Concr. Res. 40 (2010) 1052–1059,
https://doi.org/10.1016/J.CEMCONRES.2010.02.015.
[23] BIS - IS 6461: PART-7, Glossary of Terms Relating to Cement Concrete - Part VII :
Mixing, Laying, Compaction, Curing and Other Construction Aspects, Engineering
360, 1973.
[24] IS-516, Method of Tests for Strength of Concrete, Indian Standard, 1959, pp. 1–30.
[25] R. 2004, BIS:5816-1999, Splitting Tensile Strength of Concrete, Bureau of Indian
Standards, New Dehli, 2004.
[26] BS 1881-208, Testing Concrete- Part 208: Recommendations for the Determination
of Initial Surface Absorption of Concrete, 1996.
[27] ASTM C 1585-04, Standard Test Method for Measurement of Rate of Absorption of
Water by Hydraulic-Cement Concretes, 2009, https://doi.org/10.1520/C1585-
13.2.
[28] I.S, 13311(Part I), IS: 13311 (Part I) , Non-destructive Testing of Concrete Methods
of Test (Ultrasonic Pulse Velocity), Bureau of Indian Standard, 1992.
[29] X. Li, Y.M. Liu, W.G. Li, C.Y. Li, J.G. Sanjayan, W.H. Duan, Z. Li, Effects of
graphene oxide agglomerates on workability, hydration, microstructure and
compressive strength of cement paste, Constr. Build. Mater. 145 (2017) 402–410,
https://doi.org/10.1016/j.conbuildmat.2017.04.058.
[30] S. Sharma, N.C. Kothiyal, Influence of graphene oxide as dispersed phase in cement
mortar matrix in defining the crystal patterns of cement hydrates and its effect on
mechanical, microstructural and crystallization properties, RSC Adv. 5 (2015)
52642–52657, https://doi.org/10.1039/c5ra08078a.
[31] S. Lv, Y. Ma, C. Qiu, T. Sun, J. Liu, Q. Zhou, Effect of graphene oxide nanosheets of
microstructure and mechanical properties of cement composites, Constr. Build.
Mater. 49 (2013) 121–127, https://doi.org/10.1016/J.
CONBUILDMAT.2013.08.022.
[32] S. Lv, J. Liu, T. Sun, Y. Ma, Q. Zhou, Effect of GO nanosheets on shapes of cement
hydration crystals and their formation process, Constr. Build. Mater. 64 (2014)
231–239, https://doi.org/10.1016/J.CONBUILDMAT.2014.04.061.
[33] C. Lin, W. Wei, Y.H. Hu, Catalytic behavior of graphene oxide for cement hydration
process, J. Phys. Chem. Solids (2016), https://doi.org/10.1016/j.
jpcs.2015.11.002.
[34] S. Park, K.-S. Lee, G. Bozoklu, W. Cai, S.T. Nguyen, R.S. Ruoff, Graphene oxide
papers modified by divalent ions—enhancing mechanical properties via chemical
cross-linking, ACS Nano 2 (2008) 572–578, https://doi.org/10.1021/nn700349a.
[35] V. Singh, D. Joung, L. Zhai, S. Das, S.I. Khondaker, S. Seal, Graphene based
materials: past, present and future, Prog. Mater. Sci. 56 (2011) 1178–1271,
https://doi.org/10.1016/J.PMATSCI.2011.03.003.
[36] S. Lv, Y. Ma, C. Qiu, Q. Zhou, Regulation of GO on cement hydration crystals and
its toughening effect, Mag. Concr. Res. 65 (2013) 1246–1254, https://doi.org/
10.1680/macr.13.00190.
S.C. Devi and R.A. Khan
[37] S. Panzavolta, B. Bracci, C. Gualandi, M.L. Focarete, E. Treossi, K. Kouroupis-
Agalou, K. Rubini, F. Bosia, L. Brely, N.M. Pugno, V. Palermo, A. Bigi, Structural
reinforcement and failure analysis in composite nanofibers of graphene oxide and
gelatin, Carbon 78 (2014) 566–577, https://doi.org/10.1016/J.
CARBON.2014.07.040.
[38] J. Dweck, P.F. Ferreira da Silva, P.M. Büchler, F.K. Cartledge, Study by
thermogravimetry of the evolution of ettringite phase during type II Portland
12
Journal of Building Engineering 27 (2020) 101007
cement hydration, J. Therm. Anal. Calorim. 69 (2002) 179–186, https://doi.org/
10.1023/A:1019950126184.
[39] Harry F.W. Taylor, Cement Chemistry, T. Telford (1997).
[40] J.E. Rossen, B. Lothenbach, K.L. Scrivener, Composition of C-S-H in pastes with
increasing levels of silica fume addition, Cement Concr. Res. 75 (2015) 14–22,
https://doi.org/10.1016/j.cemconres.2015.04.016.