Construction and Building Materials xxx (xxxx) xxx

Contents lists available at ScienceDirect

Construction and Building Materials

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

Influence of graphene oxide on properties of concrete in the presence of

silica fumes and M-sand
P.K. Akarsh, Shriram Marathe ⇑, Arun Kumar Bhat
Department of Civil Engineering, NMAM Institute of Technology, Nitte, Karkala Taluk, Udupi District, Karnataka, India

h i g h l i g h t s

 Workability is reduced due to increased wetting water in the presence of SF and GO.
 A good dispersion of GO in the presence of ample SF and PC based superplasticizer.
 The performance of the concrete containing SF and GO satisfies PQC requirements.
 Microstructure analysis reveals a strong 3-D structure of hydration products.

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

Article history: This paper reveals the study on the use of graphane oxide (GO) in the high strength concrete contain-
Received 22 July 2020 ing silica fume (SF). The current investigations are mainly focused on the suitability of GO in SF based
Received in revised form 15 September concretes designed for pavement applications. Initially, using the Indian Standard guidelines, the con-
2020
crete mixes were designed to achieve a Pavement Quality Concrete of compressive strength 50 MPa
Accepted 24 September 2020
Available online xxxx
using conventional OPC concrete. Then, to understand the exact effect of GO, three types of concretes
were systematically developed, namely, silica fume concrete, Graphene oxide concrete and the
blended concrete containing both GO and SF; the results were compared with that of the conventional
Keywords:
Nanomaterials
concrete. Initially, the workability, compressive strength and flexural strength tests were conducted
Pavement Quality Concrete on trial mixes and based on the results the best combinations were selected for the further investi-
Graphene oxide gations. The various other tests such as compressive strength, split tensile strength, modulus of elas-
Silica fume ticity, static flexural strength, microstructure (using SEM, EDAX, XRD), durability (acid and sulphate
Strength attack test, water absorption, volume of permeable voids tests), and flexural fatigue performances
Durability were studied on selected concrete mixes. The results show that compressive strength of about
Flexural fatigue 77 MPa with a flexural strength of 8.0 MPa could be achieved for a concrete mix with 7% SF and
0.15% GO i.e., CS3G3 mix, which is way higher than the other three reference test mixes. This mix
has shown considerable performance even with other mechanical and durability performances. The
microstructure of CS3G3 mix had shown denser hydration products showing stronger bonding while
compared it with that of the other selected mixes. The results of flexural fatigue tests revealed that
the usage of GO-based concretes in association with SF can be used effectively as a pavement quality
concrete applications.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction and literature
Being an engineered material, concrete is having good compres-
sive strength but it is weak in resisting tensile stresses and flexural
stresses due to its brittle nature. When fibres are used in concrete
(i.e., Fibre Reinforced Concrete -FRC) they enhance ductility, tough-
⇑ Corresponding author.
E-mail addresses: ram.nmamit@gmail.com (S. Marathe), arun.bhat@nitte.edu.in
(A.K. Bhat).
ness and a reduction in the propagation of micro-cracks. But they
fail to resist the initiation of microcracks and they have lesser sur-
face area for hydration process. As a new perspective, the inclusion
of nanomaterial in concrete can give better result because of its
superior mechanical, chemical and electrical properties [1,2].
The size of particle plays an important role in nanotechnology
because the properties of the material can be significantly altered
at the nanolevel. In fact, at nano-level, the electrostatic forces
and quantum effect begins to prevail over gravity. The two impor-
tant aspects that enhance properties like strength, reactivity and

https://doi.org/10.1016/j.conbuildmat.2020.121093
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.

Please cite this article as: P.K. Akarsh, S. Marathe and Arun Kumar Bhat, Influence of graphene oxide on properties of concrete in the presence of silica
fumes and M-sand, Construction and Building Materials, https://doi.org/10.1016/j.conbuildmat.2020.121093
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
electrical characteristics of nanomaterials are their increased sur-
face area to volume ratio and quantum effects [3].
The application of nanotechnology and nanomaterials to con-
crete presents an innovative approach to enhance concrete prop-
erties based on the ability to modify the cementitious material at
an atomic or molecular scale. The reactions taking place in the
cement matrix depends on the smallest pores to the climatic con-
dition. Concrete has pores ranging from Nano (10 9 m) to micro
(10 6 m) scale. These pores can be minimized by good com-
paction. In spite of good compaction, some smaller pores will
remain in the cement matrix. The strength of concrete depends
on the formation of Calcium Silicate Hydrates (C-S-H) products
and products are dependent on the pores at the nano and micro
level. Filling these pores with inert or reactive material can
enhance the strength, durability properties reduce the formation
of cracks etc. When micro-level pozzolanic materials are used,
it’s only possible to fill micropores. The nanolevel pores can be
filled with the help of these nanomaterials [3,4]. As the size of
material decreases, the surface area for the reaction increases.
Nanoparticles react rapidly with Calcium hydroxide (Ca(OH)2) to
form CSH gel. This creates the denser structure and fills the pores
in the transition zone of cement [4].
Many researches have shown the incorporation of nanomateri-
als like nano-silica (n-SiO2), nano-alumina (n-Al2O3) and nano-
titanium-di-oxide (n-TiO2). In recent years, carbon nanostructures
such as carbon nanotubes (CNTs, both single and multi-walled),
carbon nanofibres (CNFs), and Graphene have attracted attention
from many concrete scholars because of their exceptional mechan-
ical, thermal, chemical & electrical properties, and use as polymeric
reinforcement materials [5]. Presently, the ideal material for nano
modification is Graphene oxide.
Graphene Oxide (GO) is a derivative of Graphene. It consists of
an extra hydroxyl group attached to the same hexagonal carbon
network. So Graphene oxide is single-layered nanomaterial con-
sisting oxygenated graphene sheets, carrying hydroxyl (OH) &
epoxy (-O-) on their basal plane and having carboxyl (COOH) & car-
bonyl (C@O) on the sheet edge. Due to the presence of these active
groups, there will be an alteration of van der Waals force between
Graphene oxide particles helping dispersion and reactivity [6–8].
Graphene oxide consists of single-layered material with carbon,
oxygen and hydrogen formed by the oxidation of graphite crystals.
The sonication damages the surface of Graphene oxide, converting
its size from micro level to nanolevel. Graphene oxide can be partly
reduced to graphene by removing the oxygen groups attached to it.
This reduced Graphene oxide is called as an r-Graphene oxide or
Functionalized graphene or chemically converted graphene [9].
However, functionalization or modification may degrade the
mechanical properties of graphene when functional groups are
introduced. Therefore, GO sheets exhibit a lower tensile strength
and elastic modulus than graphene. The mean tensile strength of
130 MPa and elastic modulus of 32 GPa is still superior to cement.
Daniel et al., (2008) [3] described the process of an aqueous disper-
sion of Graphene sheets. As Graphene is hydrophobic in nature, it is
very difficult to disperse the Graphene without the good dispersing
agent or surfactants. There is a possible stable colloidal dispersion
of Graphene using electrostatic stabilization. This will help the
large scale production of aqueous Graphene dispersion without
surfactant stabilizers. Hassani et al., (2014) [10] investigated the
performance of Graphene oxide to check whether it can enhance
mechanical and impermeability properties of cement composites
used in concrete pavements. They have used a dosage of 0.1% to
2% of GO and polycarboxylate to improve dispersion properties
by adding GO gradually to water containing superplasticizer. From
FE-SEM analysis, they observed that there was a development of
high bond strength due to nucleation of C-S-H by GO flakes. XRD
analysis revealed that there was an enhancement of C-S-H gel
2
Construction and Building Materials xxx (xxxx) xxx
which helps in permeability reduction of concrete and thereby
improving the durability of concrete pavements. Gong et al.,
(2015) [11] investigated the reinforcing effect of GO on cement
paste with optimum dosage GO of 0.03% by weight of cement
and found that there is an increase in the mechanical strength
by>40% than the ordinary matrix due to reduction of pore struc-
ture. They also observed the changes in the workability, the heat
of hydration and pore structures. They mentioned that workability
reduces with the incorporation of GO due to its high specific sur-
face area as it requires more water to wet the surface. Thermo-
gravimetric analysis (TGA) revealed that the degree of hydration
was enhanced with the incorporation of GO because of the pres-
ence of non-evaporable water and Ca(OH)2 increased as GO pro-
vides nucleation sites for hydration. Pore structure analysis
showed that there was a decrease in total porosity by 13.5%, capil-
lary pores by 27.7% and increase of gel pores by>100%. More C-S-H
products are produced which resulted in a decrease in capillary
pores and increased gel pores. Hence the addition of GO in the
cement paste fills minute pores and acts as a better nano-filler. Li
et al., (2016) [12] studied the Graphene oxide dispersion in satu-
rated Ca(OH)2 sol and cement paste. It was found that severe
aggregation occurred in the presence of divalent calcium ions
which was due to the chemical cross-linking of divalent calcium
ions. In order to counteract this situation, they have tested with sil-
ica fumes for dispersion of GO and got better mechanical proper-
ties. The two possible mechanisms could happen when Silica
fumes were added i.e. (1) Silica fumes could prevent aggregation
of GO by mechanically separating GO from calcium ions and (2)
Once GO and Silica fumes were added, the Silica fumes will react
with Ca(OH)2 to produce C-S-H products and reduce the concentra-
tion of calcium ions around GO. Silica fumes should not have over-
dosed, this would lead to the less interaction of GO with cement
hydration products because of less surface area. Thus, an appropri-
ate amount of silica fume is required for GO dispersion and for an
improved compressive strength.
Wang et al., (2017) [7] analyzed the effect of graphene oxide on
cement mortar microstructure using FE-SEM, XRD, Thermograviti-
metric techniques. They have used 0.02, 0.04, 0.06, 0.08% Graphene
oxide for analysis. At 0.08% dosage, the flexural strength and com-
pressive strength was maximum i.e. increased by 27% and 16.4%
respectively. They observed that in the low content of Graphene
oxide, the hydration products linking each other and remain diver-
gent owning to lesser nucleation sites and when dosage increased,
the hydration product tends to form clusters like structure to pre-
vent micro-cracks development. They concluded that the
microstructural changes were mainly due to the large surface area
and oxygen groups in Graphene oxide, which acts as nucleation
sites for the formation of hydration products. Li et al., (2017) [14]
used different dosages of nano-Alumina and GO to check the early
hydration and mechanical properties of cement. Both nano-
Alumina and GO enhanced the hydration process. Nano-alumina
accelerated the hydration of tricalcium aluminates (C3A) whereas
GO reduced dormant period and accelerated hydration of trical-
cium silicate (C3S). Mechanical properties enhanced in both cases
than the normal one. GO can produce large strength when com-
pared to n-Al2O3 with less % of its composition in concrete (Opti-
mum n-Al2O3-2%, GO-0.04%). They reported that, beyond
optimum value, the strength decreased due to agglomeration
nanoparticles. Lu et al., (2017) [15] investigated the effect of Gra-
phene oxide nanosheets (GONSs) on cement and ultra-high-
strength concrete in the presence of silica fumes, GGBS and super-
plasticizer. They checked fresh and hardened properties with 0–
0.03% GO by weight of cement. Fluidity decreased with increase
in GONSs content. Adding of GONSs, not only increased compres-
sive strength but also increased flexural strength and deformation
ability. Further, FE-SEM analysis gave them the result that, there
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
was a modification in the shape of cement hydration products and
GONSs was responsible for the shape modification of cement
hydration products. They concluded that the bridging of cracks
and pulling out mechanism found in CNT concrete were very diffi-
cult to identify in GONS concrete because of their low volume and
planar geometry.
GO is fabricated in a single layer or few layers made up of oxy-
genated graphene sheet. Due to the presence of oxygen functionali-
ties, the weak Vander Waals force is created between the adjacent
GO sheets whenever it’s dispersed in the solvent. So the dispersion
is easy without any surfactants. When used as a binder in cement
replacement, GO makes a covalent bond with C-S-H products and
increases the strength of cement paste. It has a large surface area
and it provides more area for the production of cement hydrates.
The production of more C-S-H gel promotes hydration due to
decrease in capillary pores and an increase in gel pores. Ultimately
it can be used as nanofiller. Many researchers have suggested the
use of superplasticizer Polycarboxylate ether is better when com-
pared to other superplasticizers. It helps in maintaining the worka-
bility and dispersion properties of Graphene oxide and silica fumes
[3,7,9,10,16].
In the presence of divalent ions like Ca2+, Mg2+ etc., the chances
of agglomeration and losing oxygen functionalities of Graphene
oxide are more. The use of Polycarboxylate ether can counteract
the situation by dispersing it. The addition of silica fumes will also
help to defend the situation by the reaction of it with Ca(OH)2.
Also, from the previous studies, it is revealed that the chances of
improvement in mechanical properties, permeability and durabil-
ity properties of cement are more when Graphene oxide is used.
The dosage required by GO is less when compared to other nano-
materials to get the same effect [14,17].
The present study focuses on the application of GO as a
nano-filler in developing a concrete utilizing M-sand for high-
way and airport-runway pavement applications. As per IRC:
15-2011 [18], the minimum flexural strength required for
any pavement is 4.5 MPa (i.e., compressive strength of
40 MPa).
Nowadays, due to increased traffic condition and varied envi-
ronmental conditions, the rigid pavements are not performing as
expected. Failures in the form of structural cracks due to combined
wheel load stresses and warping stresses, scaling and ravelling due
to loss of fine aggregates and too much abrasion, spalling etc., lead
to a deterioration of pavements.
Whenever the pavements fail to resist the fatigue cracking or
structural cracks due to repeated application of heavy wheel loads
and undesirable environmental conditions, the use of normal con-
crete leads to early deterioration of pavements. So the application
of high strength Nano modified concrete as a construction material
in such pavements may prove beneficial. The advantage of the use
of such high performance concretes can suppress the material cost
by reducing the thickness of pavement slab or by saving material
requirement. Following were the specific objectives and scope of
the present study:
Table 1
Laboratory test results of Cement.
Property Results
Retained 90 mm (Fineness Modulus) <1%
Standard consistency 34%
Initial setting time 80 min
Final setting time 330 min
Soundness by Le-Chatelier’s <1 mm
Specific Gravity by Le-Chatelier’s 3.15
3
Construction and Building Materials xxx (xxxx) xxx
 To study properties of concrete with the inclusion of Graphene
oxide and silica fumes and there-by obtain the mechanical per-
formance of Nano modified concrete designed for pavement
applications.
 To study the microstructural behaviour of selected GO-SF based
concrete mixes through SEM-EDAX and XRD analysis.
 To determine the durability performance of nano-modified GO-
SF based concrete mixes after subjecting it to sulphate and
acidic environments.
 To determine the Flexural fatigue performance of nano-
modified GO-SF based concrete mixes and thereby checking
the suitability of the same for high strength rigid pavements.
2. Materials and methodology
2.1. Materials
 Cement: Cement used in the study was 53-grade Ordinary Port-
land Cement in accordance with IS 12269-2013 [19]. It was pro-
cured from a reputed cement producing company practising
advanced quality production and guaranteed chemical compo-
sition of cement. Initial investigation and laboratory tests were
carried out on cement as obtained from the supplier, to assess
the physical requirements. The results of the test are shown
in Table 1.
 Aggregates: Aggregates are procured from M/s Oriental Gran-
ites and Crushers, Karkala taluk, Udupi. Aggregates used are free
from organic impurities. Coarse aggregates used are crushed
angular type and well-graded as per IS 383-2016 [25]. Table 2
shows the quality test results of coarse aggregates. The fine
aggregates used are manufactured sand. Table 3 shows the
properties of M-sand and it conforms to Zone II of IS 383 having
a fineness modulus of 2.5.
 Superplasticizer: Superplasticizer was procured from Fosroc
Chemicals India Pvt. Ltd. The chemical called ‘Auramix 400
PQC’ was used which is a high performance based superplasti-
cizer conforming to IS 9103-1999 [28]. The dosage recom-
mended by the company is 0.3 to 1.2% by weight of cement. It
was mixed with a sufficient amount of water and added during
the concrete mixing.
 Silica fumes (SF): It was procured from Corniche India Pvt. Ltd.
The use of silica fumes is most preferable for pavements where
abrasion resistance is required. As per IRC 15-2011 [18] and IRC
114-2013 [33], the preferred dosage is 3–10% by wt. of cement.
For the current project, the varied dosage of 3%, 5%, 7% and 10%
of silica fumes by weight of cement were used. Table 4 shows
the specification of the material conforming to IS 15388–2003
[31].
 Graphene oxide (GO): Graphene oxide is obtained from ‘‘Ad-
Nano Technologies Private Limited”. The company has limited
the amount of Graphene Oxide to be dispersed in water to a
maximum of 7 g/litre of water (i.e. 0.7% solution). Beyond that
dosage, surfactants are required or sonicator is required for
Limits as per IS 12269-2013 Test method
Max 10% IS 4031(P1)-1996 [20]
– IS 4031(P4)-1988 [21]
Min 30 min IS 4031(P5)-1988 [22]
Max 600 min
Max 10 mm IS 4031(P3)-1988 [23]
– IS 4031(P11)-1988 [24]
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

Table 2
Laboratory test results of Coarse Aggregates.

Property Test Results Limits Reference Code Test method

Strength Aggregate Crushing Value 27.5% <30% IS 383-2016 [25] IS 2386 (P4) 1963 [26]
Toughness Aggregate Impact Value 16.8% <30%
Abrasion Los Angeles Abrasion Value 30% <35% IRC 15 2011 [18] and MORTH Clause No: 602.2.6.1
Shape Combined flakiness and elongation 22.4% <35% IRC 15 2011 [18] and MORTH Clause No: 602.2.6.1 IS 2386 (P1) 1963 [27]
Quality Specific Gravity 2.69 – –
Water absorption Water absorption 0.5% Max 2% MORTH Clause 602.2.6.2

Table 3
Laboratory test results of Fine Aggregates.

Test Results Limits Reference code Test Method

Specific Gravity 2.62 – – IS 2386 (P3) 1963 [27]
Water absorption 1.5 Max 2% IRC 15 2011 [18]
Particle passing 75 mm 2.6% Max 15% IRC 15 2011 [18] and IS 383–2016 [25] IS 2386 (P1) 1963 [29]
Soundness (Weight loss after 5 cycles) 2.13 Max 12% IRC 15 2011 [18] IS 2386 (P5) 1963 [30]
Sodium Sulphate 2.73 Max 18%
Magnesium Sulphate

Table 4 2.2. Methodology of work

Properties of Silica Fume.

Property Material Limits as per IS 15388–2003 [31]  Fixing of w/c ratio and superplasticizer dosages: The decision
Specification and ASTM C 1240 [32] regarding the w/c ratio is done considering the workability and
SiO2 92.3% 85% min strength requirements. Mix design was done as per IRC: 44–
Loss on Ignition 1.8% 6% max 2017 [34]. Various trial mixes with different w/c and different
Pozzolanic Act Index 127% 105% min
Specific Surface Area by 22 m2/gm >15 m2/gm
superplasticizer dosages were conducted to get optimum work-
BET analysis ability of 25–50 mm and desirable strength. The slump test is
Moisture 0.2% 3% max adopted to check the workability. Basically, for trial purpose
Bulk density 678 550–700 Kg/m3 and to know the dosage capacity of Superplasticizer, at first
Passing 45 mm 0.3% 10% max
the use 0.38 w/c was done. To attain the required grade of con-
Specific Gravity 2.2 –
crete, w/c was adopted as 0.35 and checked for the slump. Fig. 1
shows the slump result. For conventional concrete, a dosage of
0.6% Superplasticizer and w/c 0.35 is fixed based on the results
Table 5
Properties of Graphene oxide.
obtained. Further, the cubical moulds of side 100 mm conform-
ing to IS: 10086–1982 [35] were prepared and the compressive
Property Material Specification strength were checked for different aggregate ratios. Since the
Surface area 200 m2/gm voids filling property in the matrix is very important to attain
Average thickness (Z) 1–4 nm the required strength this trial is done. The selection of aggre-
Average Lateral dimension (X&Y) 5–10 mm
Bulk density 0.1 g/cc
gate ratio was done with sustained w/c of 0.35. Two coarse
aggregate fractions of size 20 mm and 10 mm were used with
different ratios in order to check 7-day compressive strength.
Table 6 shows test results, which reveals that for the further
proper dispersion. For good dispersion, the company has recom- progress of the work, the w/c of 0.35, superplasticizer dosage
mended 0.1–0.5% by weight of cement. For current research, a of 0.6% and 60:40 aggregate ratios which give maximum com-
dosage of 0.05%, 0.1%, 0.15% and 0.2% by weight was adopted. pressive strength (highlighted in Table 6) remains constant for
The specifications are shown in Table 5. all the further mixes.

Fig. 1. Slump test result for different SP dosage.

4
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
Table 6
Compressive strength for different aggregate ratios.
Sample Aggregate ratios 7 day Compressive Strength in
no. (20 mm:10 mm) MPa
1 80:20 39.23
2 75:25 41
3 70:30 42.8
4 60:40 44
 Preparation of Graphene oxide solution: Graphene oxide in
powder form is used to make an aqueous solution. Due to its
oxygen functionalities, it can be dispersed without any surfac-
tants. As per the supplier company’s guidelines, the magnetic
stirrer was used to make a solution (Probe sonicator, the ideal
one to make solution). In magnetic stirrer, the magnetic field
is applied in order to rotate the ‘Stir bars’. The rotation speed
of the stir bar mainly depends on rotating magnet in the stirrer
device. The used stirrer has the capacity to rotate at speed rang-
ing from 600 to 1000 rpm. To improve the adhesion property of
graphene oxide, the superplasticizer is mixed with water ini-
tially in stirring equipment and calculated quantity of graphene
oxide is added slowly to the rotating mix. In the first few min-
utes, the rpm maintained was less and after 4–5 mins, the rpm
is set to maximum for 7–10 min. A black solution containing
graphene oxide along with the superplasticizer shown in
Fig. 2, obtained is added to the concrete mix. The solution water
is subtracted from total quantity water required to prepare the
concrete mix.
2.3. Mix proportion design details
To know the effect of Graphene oxide, the three types of con-
crete mixes were studied (other than the conventional mix), silica
fume concrete, Graphene oxide concrete and concrete containing
both silica fumes and Graphene oxide and all the mixes are com-
pared with the ordinary conventional cement concrete. The main
intention of the work is to analyze the effect of Graphene oxide
in the presence of silica fumes and suitability of it as high strength
concrete pavements.
Fig. 2. Preparation of GO solution using Magnetic stirrer.
5
Construction and Building Materials xxx (xxxx) xxx
 Conventional concrete mix: The mix design for conventional
concrete for pavement applications were developed based on
the procedure suggested for designing the mix proportions for
conventional OPC based Pavement Quality Concrete as per
IRC: 44-2017 [34] which is in line with conventional concrete
mix-design code IS: 10262-2009 [36]. In this work, the design
was done for M-50 grade of concrete using a total binder
content of 440 kg/m3, with water/binder ratio of 0.35 with a
superplasticizer (SP) dosage of 2.64 kg/m3 and fine aggregate:
coarse aggregate ratio of 0.36:0.64. The mixes were designed
to achieve a slump value of 25–50 mm.
 Silica fume concrete mix: In this concrete mix, the silica fumes
(SF) is replaced by the weight of OPC like 3%, 5%, 7% and 10%.
The details are given in Table 7.
 Mix design for Graphene oxide concrete: In this concrete mix,
the Graphene oxide is added by weight of OPC like 0.05%, 0.1%,
0.15% and 0.2%. The details are given in Table 8.
 Mix Design containing both Graphene oxide and silica
fumes: In this section, the test result of concrete containing
both silica fumes and graphene oxide is presented. The details
are given in Table 9.
2.4. Mixing of materials, casting and curing
The appropriate quantities for the required mix were batched.
For conventional concrete, coarse aggregate, fine aggregate and
Cement were thoroughly dry mixed in an electrically driven mixer
and superplasticizer was added as per IS 516:1959 [37]. Silica fume
concrete was prepared based on the guidelines given in Silica
fumes user’s manual, U.S Department of Transportation for labora-
tory mixes [38]. While preparing Graphene oxide concrete, the
water used for making GO solution was deducted from overall mix-
ing water.
In order to make concrete containing both SF and GO, initially
coarse aggregate and 25% of water + silica fumes were added to
the electrically driven mixer and mixed for about 3 min. Then thor-
oughly dry mixed cement and fine aggregate is added with the
remaining water and mixed for 3–4 min. After 3–4 min of mixing,
superplasticizer containing GO solution is added. For uniform
blending and dispersion of Graphene oxide, the mix was mixed
for another 2 mins.
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

Table 7
Mix Proportion details of Silica fume concrete in kg/m3.

SF % (by weight) Mix ID Cement Water Coarse aggregate M-sand SP SF

0 CC 440 154 1190 680 2.64 0
3% CS1 427 154 1190 680 2.64 13
5% CS2 418 154 1190 680 2.64 22
7% CS3 409 154 1190 680 2.64 31
10% CS4 396 154 1190 680 2.64 44

Table 8
Mix Proportion details of Graphane Oxide concrete in kg/m3.

GO % (by weight) Mix ID Cement Water Coarse aggregate M-sand SP GO

0 CC 440 154 1190 680 2.64 0
0.05% CG1 440 154 1190 680 2.64 0.22
0.1% CG2 440 154 1190 680 2.64 0.44
0.15% CG3 440 154 1190 680 2.64 0.66
0.2% CG4 440 154 1190 680 2.64 0.88

Table 9
Mix Proportion details of Concrete with both GO and SF in kg/m3.

SF % Mix ID OPC Water Coarse Aggregates M -sand SP SF GO

0 CC 440 154 1190 680 2.64 0 0
3% CS1G1 427 154 1190 680 2.64 13 0.22
CS1G2 427 154 1190 680 2.64 13 0.44
CS1G3 427 154 1190 680 2.64 13 0.66
CS1G4 427 154 1190 680 2.64 13 0.88
5% CS2G1 418 154 1190 680 2.64 22 0.22
CS2G2 418 154 1190 680 2.64 22 0.44
CS2G3 418 154 1190 680 2.64 22 0.66
CS2G4 418 154 1190 680 2.64 22 0.88
7% CS3G1 409 154 1190 680 2.64 31 0.22
CS3G2 409 154 1190 680 2.64 31 0.44
CS3G3 409 154 1190 680 2.64 31 0.66
CS3G4 409 154 1190 680 2.64 31 0.88
10% CS4G1 396 154 1190 680 2.64 44 0.22
CS4G2 396 154 1190 680 2.64 44 0.44
CS4G3 396 154 1190 680 2.64 44 0.66
CS4G4 396 154 1190 680 2.64 44 0.88

The mixed samples were cast in appropriate moulds. Since the
w/c is less, the vibrating table method was adopted for com-
paction. Moulds are filled in a minimum of 3 layers and vibrated
for 5–10 s. The top layer is finished by giving a smooth finish
and allowed to set without disturbance. The samples are de-
moulded by allowing it set for a minimum of 16 hrs after casting.
The samples are cured for a stipulated duration at 27 ± 3 °C. The pH
of the water was maintained at 6–8.
2.5. Testing of concrete mixes
 Fresh properties test: As the consistency of mix very important
at the site, the flow or workability properties of the freshly pre-
pared mixes were tested by slump cone apparatus. The test was
carried out to compare the consistency of conventional mix pre-
pared with w/c 0.35 and test specimens. It was carried out as
per IS 1199:2018 [39].
 Hardened properties test: The tests on compressive
strength, split tensile strength, Modulus of Elasticity, flexural
strength were performed in order to understand the con-
crete’s hardened state properties. All the tests were per-
formed as per the guidelines suggested by the respective
Indian standards [37,40,41]. In-addition, Saturated Water
Absorption (SWA) and Volume of Permeable Voids (VPV)
are conducted based on the procedure given in ASTM
C642-13 [42].
 Microstructure analysis: To analyse the surface morphology of
the concrete, Scanning Electron Microscopy (SEM) is used. Fur-
ther, the X-ray Diffraction technique (XRD method) is used as a
rapid analytical method to identify the crystalline phases of the
material. When X-rays are subjected to the materials, the mate-
rial diffracts the X-rays at a particular diffraction angle (2h) and
gives unique diffraction patterns. Whenever that material is in a
mixture of many substances, it will give its diffraction pattern, if
it’s present in that mixture. The diffraction angle is different for
different material. Therefore the output will be like a fingerprint
of each material.
 Durability test: The selected concrete specimens were sub-
jected to intense acidic and sulphate environment and their
performance was studied. In order to check the acid attack,
the concrete specimens of 100 mm  100 mm  100 mm were
immersed in 5% Sulphuric acid solution (5 ml of 0.1 N Conc.
H2SO4 in 100 ml of water). After the specimens are cured in
water for 28 days, they are immersed in acid solution and tested
at 56 and 90 days. The pH of 5% solution is constantly main-
tained between 1.9 and 3.2. The test involves noting down the
weight change and strength change after immersion in the solu-
tion at 56 and 90 days. Totally 24 cubes are used for this test (6
cubes for each mix). Similar to acid attack test, sulphate attack
tests were performed by immersing the similar concrete cubes
in a solution of 5% Magnesium sulphate (5 g of MgSO4
7H2O in
100 ml of water).

6
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
 Flexural Fatigue test: Fatigue failure is one of the major failures
in the structure like concrete pavements and occurs over a long
period due to repeated movement of heavy traffic vehicles and
high-intensity movement. The fatigue failures in concrete pave-
ments occur at the repetitive load or cyclic loads in such a way
that whose peak stress values are considerably less than the
safe load estimated in static flexural strength. For the current
investigation, the loads are applied in repeated cycles to cause
the failure of concrete beams at stress less than the maximum
value of the strength of beams. The prism of dimension
100 mm  100 mm  500 mm were cast and tested after
28 days of curing. A total number of 40 prisms containing 10
prisms for each best combination were used. The tests were
conducted on Fatigue testing machine manufactured by Sprank-
tronics.Ltd, Bengaluru having load cell capacity of 5 tonnes.
3. Results and discussions
3.1. Results on silica fume concrete
The slump results have shown that, as the silica fume dosage
increases from 0% to 10%, the mix was stiffer and the slump value
decreased gradually from 50 mm till 30 mm. This may be possibly
due to the higher specific area of the silica fume which needs a
higher wetting water requirements [16,43]. The 28-day compres-
sive strength results on the same mixes indicated that the com-
pressive strength of specimens gradually increased with an
increase in silica fume dosage. Further, the maximum strength of
70.33 MPa was achieved for CS3 mix with 17% increment with
respect to CC mix. The similar results were seen for the flexural
strength test. This is due to micro-filling of voids in between the
transition zones (physical effect) and calcium hydroxide formed
is converted to calcium silicate hydrates by silica fumes (Chemical
effect) [10,44]. The improved strength of the SF based concrete can
be attributed to the formation of a strong inhibiting layer of the
secondary hydration products due to the reaction between the SF
and calcium hydroxide [43,45].
3.2. Results on graphene oxide concrete
The slump test results revealed that there is a 20% reduction in
the slump value for CG4 mix while compared it with that of the CC
mix. Since the surface area of GO is more, it consumes more water
for wetting its surface [1]. Therefore the slump value shows down-
ward value as the dosage increased. But the loss of workability is
not so significant and can cope up with the help of superplasticizer.
The role of superplasticizer is very significant in nano-concrete as
it will help in the dispersion of nanomaterial and also maintaining
the consistency [17].
Compressive strength test results showed that, as the dosage of
Graphene oxide increases, the compressive strength increases up
to a particular point and later on it will decrease due to inadequate
dispersion. In this scenario, the CG3 specimen shows the highest
compressive strength (68 MPa) while compared with CC
(59.67 MPa) because of proper dispersion. The CG4 shows lesser
strength (64.67 MPa) than the CG3 because of formation of GO
cluster. Ultimately clusters leading to the formation of voids. Sim-
ilar results were seen in flexural strength results i.e., 6.03 MPa for
CC to 6.90 MPa for CG4 mix. In both the cases, from the 7-day
strength, it was clear that, the percentage early gain in strength
at 7 days was more (about than 85% of 28-day strength) than
later-age strength, which is helpful for the application of pave-
ments. This improvement in the compressive and flexural strength
is due to the accelerated hydration C3S of the GO-cement paste,
leading to the development of the increased nucleation sites pro-
7
Construction and Building Materials xxx (xxxx) xxx
vided by the large surface area of GO; this also leads to the devel-
opment of the secondary hydration peaks [14].
3.3. Mechanical strength on mix containing both Graphene oxide and
silica fumes
 Compressive strength: From Fig. 3, the concrete with 0.15% GO
addition and 7% silica fume replacement shows the greater
strength improvement at both 7 and 28 days when compared
to all the combinations concerned. Silica fume concrete speci-
men CS3 and Graphene oxide concrete specimen CG3 gave a
compressive strength of 70.33 MPa and 68 MPa respectively
at 28 days. But the best combinations of both gave a compres-
sive strength of 77.33 MPa. This shows that GO could act better
in the presence of silica fume and PC based superplasticizer. In
the presence of both silica fumes and PC based superplasticizer,
two possible reactions could happen, (1) Silica fume reacts with
excess calcium hydroxide, which helps in stabilization of GO
and proper dispersion of GO [46] and (2) Steric hindrance effect
of PC based superplasticizer, which means it will push the GO
sheets away from each other to disperse properly all along with
the matrix [10]. On the other hand, the things will be easy for
GO sheets; the covalent bond formed with calcium silicate
hydrates helps the concrete to become stronger [47]. Moreover,
the dispersion helps in filling of nano and micro level voids in
concrete [2,46]. Ultimately, the concrete designed is beneficial
for the worse environmental condition.
 Flexural strength: From compressive strength test results, the
effect of 0.05% GO and 0.2% GO in the presence of silica fumes
was not so much significant. Hence only 0.1% GO and 0.15%
GO is varied in combination with silica fume for finding the
optimal dosage of GO. From Fig. 4, CS3G3 specimen shows a
greater flexural strength improvement than all than specimens
concerned. This is because the dispersion of nano-material is
key to obtain higher and higher superior properties. The pres-
ence of silica fume and superplasticizer is very much beneficial
for this act. The dispersion will reduce the formation of agglom-
erates ultimately the voids [7,17]. The concrete containing both
silica fumes and graphene oxide shows a greater flexural
strength (7.9 MPa) than the silica fume concrete (7.1 MPa)
and graphene oxide concrete (6.9 MPa) at 28 days respectively.
In all the three types of concrete, the percentage early increase
in strength is more than the later strength. This is very much
favourable for the application of pavements. Moreover, all the
three concretes qualify for the minimum strength requirement
criteria prescribed in IRC: 15–2011 [18].
 Other Tests: The results obtained from compressive strength
test and flexural strength test, the CS3 specimen from silica
fume concrete, CG3 specimen from graphene oxide concrete
and CS3G3 specimen from concrete containing both silica fume
and graphene oxide were taken as optimum dosage from each
of the specified concrete types. The further investigations like
spilt-tensile strength, cylinder compressive strength, modulus
of elasticity, Test for water absorption and Volume of Permeable
Voids (VPV), Microstructural analysis using SEM, XRD analysis,
Energy Dispersive Analysis by X-ray (EDAX), Durability (Acid
and sulphate attack), and Flexural Fatigue tests were conducted
are for these selected optimum percentages.
 Compressive strength of cylinders: The CS3 specimen shows
greater strength than the CG3 specimen because silica fumes
not only fill the micropores, it will help in the hydration process
also [16,43]. Moreover, dispersion of GO will be complicated
than the silica fumes. When compared to other specimens,
CS3G3 shows larger strength because of better nano and micro-
voids filling. Whenever the pores are filled, the concrete
becomes denser and stronger [2,14]. Moreover, the combined
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

Fig. 3. Compressive strength of CSG specimen at 7 and 28 days.

Fig. 4. Flexural strength of CSG specimen at 7 and 28 days.

Table 10
Test results on Cylinder Compressive Strength, Split-Tensile Strength, and Modulus of Elasticity of Selected Mixes.

Mix name Mix constituent Cylinder Compressive Strength (MPa) Split Tensile Strength Modulus of Elasticity (GPa)
(MPa)
7 Day 28 Day
Conventional 0% 40.67 2.92 4.315 31.247
CG3 7% SF 44.06 3.10 4.39 32.060
CS3 0.15%GO 46.89 3.24 4.485 33.109
CS3G3 7% SF & 0.15% GO 50.28 3.47 4.67 34.175

effect of silica fumes and superplasticizer on GO helps to
strongly resist the compressive stresses. Results were depicted
in Table 10.
 Split tensile strength test: Overall, the percentage increase in
the 7 days strength is more than the 28 days strength. CS3 spec-
imen gives greater value than the CG3 because, in GO concrete,
there is a possibility of formation of agglomeration and that will
leads to the formation of voids, resulting in lesser strength [10].
CS3G3 specimen shows more tensile strength than all the spec-
imens because of better voids filling capability. In CS3G3 spec-
imen, due to proper dispersion of GO with the help of silica
fumes and superplasticizer, one can see the bonding between
the GO sheets and calcium silicate hydrates. Ultimately, the for-
mation of a cluster of GO sheets will be reduced. When tensile
stresses are applied, GO shows breakout mechanism and not
the pull out mechanisms [10]. The increased compressive and
tensile strength of GO-based concretes is attributed to the
‘‘bridging” action of GO sheet inside the concrete structure,
which lead to powerful and stable hydration products [13]. Test
results are shown in Table 10.

8
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

 Modulus of Elasticity: The specimen containing both the
SF and GO shows higher ‘E’ value than all the specimens
because it can take more stress with lesser deflection and
microstructural enhancement of concrete [17]. Whenever the
force is applied, the GO nanosheets distribute the stresses in a
nano-level uniformly if it’s properly distributed all over the
matrix. All specimens prepared to qualify the minimum
requirement of modulus of elasticity specified in IRC: 15–
2011 i.e. 30 GPa [18]. Test results were indicated in Table 10
 Saturated Water absorption (SWA) and Volume of Permeable
Voids (VPV): The strength and durability properties are depen-
dent on the water absorption and permeable voids. The tests
were conducted after 28 days of curing. The CG3 shows a lesser
value than the CS3 specimen. This is because graphene oxide
improper dispersion and cluster create larger voids. Thus larger
voids will result in larger %SWA and VPV%. The CS3G3 specimen
shows least SWA % and VPV% when compared to other speci-
mens. This is because graphene oxide is in nanoscale and silica
fume is at the micro-level. So the voids in these scales are filled
with these materials. Automatically, the water absorption and
VPV will decrease and other durability properties improve.
The main advantage of the GO is the presence of oxygen func-
tionalities. Along with that, if the usage of any dispersion tech-
niques is adopted, one can expect better results from the
nanomaterial [3,9]. The results were indicated in Table 11.
The summary of the key results of the mechanical strength of
the concrete mixes is shown in Table 12.
3.4. Microstructural analysis of selected mixes
3.4.1. SEM analysis
The SEM image of the fracture surface of Conventional concrete
(CC) specimen after 28 days curing is shown in Fig. 5. Basically, it
shows the fundamental hydration products, such as needle-like
ettringite (AFt phases), laminated calcium hydroxide (Ca(OH)2)
and fibrous or hairy Calcium silicate hydrates (C-S-H), inter transi-
tion zone (ITZ) between cement hydrates and aggregates at the
scale of 10 lm. In Fig. 5(b), the fibrous CSH and needle-like AFt
phases are seen at a scale of 1 lm [48].
Fig. 6 shows a similar aged SEM image of concrete chunks of CS3
specimen. Similar to the conventional concrete, the dense hydra-
tion products are observed all over the matrix taken at a scale of
2 lm. The image shows coarse aggregate at one part and hydration
products, inter-transition zones on other parts. The calcium silicate
hydrates are one of the most desirable hydration products which
are spread like a dense sponge-like structure [48] that gradually
spread and adhered to the surface of silica fumes. The silica fumes
play a very important role in the hydration process as it consumes
the excessive calcium hydroxide and converts it to the calcium sil-
icate hydrates (C-S-H) gel. Being a microparticle, the silica fume
provides nucleation sites for C-S-H gel and helps in accelerating
the hydration process [43]. This may be the reason for the early
gain in compressive strength and flexural strength. Silica fume acts
like a micro filler in the concrete matrix. Despite that, some of the
nanolevel pores are visible in the CS3 specimen. These pores are
formed mostly due to improper dispersion and inefficient mixing
procedure [44].
Fig. 7 shows the SEM image of a fracture portion of GG3 speci-
men after 28 days of curing. It shows the aggregate covered with
the dense hydration products and the hydration products appear
to be quietly undistinguished due to densely formed microstruc-
ture scanned at a scale of 10 lm. Some of the cracks are also visible
in the image, showing a lot of stress is taken by the specimen. The
dense microstructure may be due to well bonding between GO and
cement products. Comparing with Figs. 5 and 6, the shape of
hydration products has changed in Fig. 7. This may be due to the
presence of GO sheets. For the current investigation, the usage of
GO is very less, it’s very difficult to find the GO sheets in the
specimen. Either, the hydration product may cover the GO or due
to its planar geometry, difficult for identification. Compare to CS3
specimen, the CG3 shows comparatively less flexural strength
due to the formation of clusters or agglomerates in the inter-
transition zones [7]. This could be minimized by using an efficient
mixing technique.
The Fig. 8(a) shows an SEM image of chunk piece of CS3G3 spec-
imen. In this figure, the needle-shaped ettringite is mostly seen
and widely spread dense sponge matrix of C-S-H is seen at a scale
of 2 lm. The calcium hydroxides are also seen in the form of lam-
inated sheets. Due to the presence of silica fumes, microvoids are
filled and some of the calcium hydroxides have been converted
to C-S-H gel. This will lower the Vander walls force between the
GO sheets and stabilizing it to disperse uniformly all along with
the matrix without promoting to the formation of clusters. Fig. 8
(b) shows an enlarged view of the particular section showing sharp
needle-shaped AFt phases and thick fibrous C-S-H at the scale of

Table 11
Results on Water Absorption and VPV.

Mix name Oven dry mass Saturated mass Water absorption % = (B- Boiled and surface dried Mass in water Volume of permeable voids = (C-
‘A’ in g ‘B’ in g A)*100/A weight ‘C’ in g ‘D’ in g A)*100/ (C-D)
Conventional 2.522 2.601 3.132 2.602 1.575 7.79
CS3 2.534 2.611 3.039 2.611 1.555 7.3
CG3 2.530 2.607 3.043 2.610 1.565 7.66
CS3G3 2.553 2.623 2.742 2.629 1.575 7.212

Table 12
Summarized Test Results of Best Combination Concrete.

Name of Tests conducted at 28 days of curing Mix ID

Conventional CS3 CG3 CS3G3
Compressive strength of cubes 59.67 MPa 70.33 MPa 68 MPa 77.33 MPa
Static flexural strength of prisms 6.1 MPa 7.1 MPa 6.9 MPa 8.0 MPa
Split tensile strength of cylinders 4.315 MPa 4.485 MPa 4.39 MPa 4.67 MPa
Modulus of elasticity of cylinders 31.2GPa 33.2GPa 32.1 GPa 34.2 GPa
Compressive strength of cylinders 40.7 MPa 44.1 MPa 46.9 MPa 50.3 MPa
Water absorption test 3.132% 3.039% 3.043% 2.742%
Volume of permeable voids 7.79% 7.3% 7.66% 7.212%

9
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

Fig. 7. SEM image of CG3 specimen at 28 days.

Fig. 5. (a) SEM image of Conventional concrete at 28 days (b) Enlarged view
showing fibrous C-S-H and Ettringite.

Fig. 6. SEM image of CS3 specimen at 28 days.

1 lm. The thick fibrous C-S-Hs, most desirable hydration products

gradually spread, merge, adhered to the GO (seen in Fig. 8 (b))
which helps in strengthening and lowering the permeability. There
is a good bonding between the cement particles and GO. Usually,
C-S-H and ettringite are seen in pores between the zones. If these
pores are filled by micro and nanomaterial, they will accelerate the
hydration process due to nucleation of hydration products [44,49].
Further, the dense microstructure of CS3G3 is due to the formation
of a strong three-dimensional structure of hydration products
through a reaction between calcium hydroxide and GO particles,
which further leads to an improvement in the mechanical perfor-
mance of the mixes [6].
Fig. 8. (a) SEM image of CS3G3specimen at 28 days (b) Enlarged view showing GO
sheet, C-S-H and Ettringite in CS3G3specimen.
3.4.2. XRD analysis
The X-ray diffractogram is a graph plotting 2h angle on the x-
axis against the diffraction intensity on the y-axis. The originPro
2018 software was used in order to draw the image from respec-
tive diffraction angles. The X-ray diffractogram of powdered con-

10
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
crete specimens with the best 4 combinations is shown in Fig. 9(a),
(b), (c) and (d).
With the help of Xpert Highscore Plus, it can detect the miner-
alogy or crystalline phases shown by those intense peaks. Too
many intense peaks were observed in Fig. 9(a) (conventional con-
crete). It is a well-known fact that 70 to75% of concrete contains
aggregate, thus the larger intense peaks mostly of Silicon-di-
oxide (SiO2) or quartz. The SiO2 peaks majorly seen at 2h angle of
20.850°, 26.640° and 50.139° with co-ordinates (1,0,0), (1,0,1)
and (1,1,2) respectively and scale factor of 0.345. The calcium car-
bonate (CaCO3) phases are detected at 2h angle of 29.406°, 39.402°
and 48.514° with coordinates (1, 0, 4), (1, 1, 3) and (1, 1, 6) respec-
tively and scale factor of 0.049. The possible reason for the pres-
ence of CaCO3 is it’s one of the principal raw material of cement
or the reaction between the free calcium oxide with plenty of sul-
phate source giving CaCO3 or calcium minerals like ettringite.
Another possible reason for the presence of calcium carbonate is
the carbonation of calcium bearing hydration products like CSH,
portlandite and ettringite which reacts with carbon dioxide to form
calcium carbonate [50]. Other than these peaks, no other signifi-
cant peaks were able to detect in that software.
The diffractogram of CS3 specimen is shown in Fig. 9(b) indicate
no major changes in the intensity of peaks. As usual, SiO2 peaks are
seen at the same diffraction angle but CaCO3 phases are diffracted
at a larger scale of 0.254. The increase in factor shows the increase
in hydration process due to the presence of silica fumes. So the
(a) Conventional concrete specimen
(c) CG3 concrete specimen
Fig. 9. X-ray Diffractogram figures.
11
Construction and Building Materials xxx (xxxx) xxx
concrete shows more strength than the conventional one. The
Fig. 9(c) shows the diffraction pattern of CG3 specimen which also
illustrate no peaks corresponding to Graphite compound.
The Fig. 9(d) shows the XRD of CS3G3 specimen. The intensity
peaks observed are much higher when compared to the other test
specimens. In this figure, due to the presence of quartz, the peaks
at 26.640° and 50.141° are observed. Many peaks are observed
due to an increase in the hydration products, which is due to the
combined effect of silica fumes and graphene oxide. On one side,
the silica fumes convert calcium hydroxide to calcium silicates
and on the other side, the graphene oxide acts as nucleation sites
for produced calcium silicates [45,46]. Due to smaller dosages of
GO content used in the concrete and some instrumentation limita-
tions, the peaks corresponding to graphite containing compound
were not observed.
3.4.3. Energy Dispersive analysis by X-ray (EDAX)
The EDAX study is carried out on only conventional (Fig. 10) and
CS3G3 concrete (Fig. 11) specimens after 28 days of curing. The
results give information regarding the cement hydration and their
percentage constituents. The difference in results shown in Figs. 10
and 11 indicates the increase in calcium and oxygen constituents
by CS3G3 concrete specimen. The increase in calcium may be
attributed to an increase in C-S-H gel, which is mainly due to the
combined effect of silica fumes and graphene oxide. The increase
in oxygen may be attributed to the presence of a strong oxide com-
(b) CS3 concrete specimen
(d) CS3G3 concrete specimen
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
Fig. 10. EDAX graph of Conventional concrete specimen with % constituents.
pound in the system - either it may be silica fumes or graphene
oxide. So ultimately, the properties of this nanomaterial can be
explored efficiently in the presence of silica fumes.
3.5. Durability of optimum mixes
In the current investigation, the weight loss and strength loss
(up to 90 days) has been studied after subjecting the selected spec-
imens (CC, CS3, CG3 and CS3G3) to severe sulphuric acid attack and
sulphate attack, kept after 28 days of curing.
3.5.1. Acid attack test
Upon 28 days of immersion in 5% H2SO4 solution, the outer sur-
face of cubes leached with soft white material and it was washable.
After 56 days immersion, the strength and weight gradually
decrease due to the formation of excessive gypsum at reaction area
[51]. The first layer is completely deteriorated or spalled due to
acid attack. Further, it was observed that, even though the mixes
show spalling, they have the capacity to restrain the compressive
strength. The CS3G3 specimen takes larger stress when compared
to other mixes. The complete chemical reaction is not known
exactly. When cubes tested after 90 days, the cubes appeared as
shown in Fig. 12. The weight loss and strength loss were observed
as revealed in Table 13. Due to acid penetration and at high acid
content, the hydration products have been damaged and led to a
12
Construction and Building Materials xxx (xxxx) xxx
partial deterioration of concrete cubes. The strength and the
weight reduction are due to the permeation of the acid particles
through the micropores which dissociate the hydration products
of the concrete. The sulphuric acid particles will react with the cal-
cium hydroxide particles to form gypsum, which further leads to
the deterioration of the concrete due to the formation of ettringite
[51].
3.5.2. Sulphate attack test
As tested after 56 days immersion in 5% magnesium sulphate
solution, the weight change or strength loss or change in the shape
in cube or change in colour of the cube were not so significant as
shown in Fig. 13. Due to better pore refinement, the concrete
doesn’t allow sulphate solution to enter into the system at 56 days.
When tested after 90 days, the cubes shows a gain in strength
and strength loss is quite significant than the tested at 56 days.
After continuous immersion of cubes for 90 days, cubes show some
weight gain. But no visible expansion or gypsum formation on the
surface was observed. The strength loss is due to alteration in
hydration products. The specimen containing both silica fumes
and GO shows better defence against the magnesium sulphate by
showing less change in weight and less change in strength. The
concrete shows good resistance against the sulphate attack as
there are less weight change and strength loss. The results are
in-line with the findings from Diab et al (2019), who reported that
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

Fig. 11. EDAX graph of CS3G3 concrete specimen with % constituents.

Fig. 12. Surface deterioration of cubes after 90 days of immersion in 5% sulphuric acid.

the high porosity in concrete specimens leads to easier destruction
due to sulphate attacks; the adding of more percentage of nanoma-
terials can reduce the permeability of concrete specimens and the
corresponding decreases in the loss in strength and weights upon
continued exposures [52]. The results are shown in Table 14.
13
3.6. Flexural fatigue test results
The fatigue tests were conducted on the beam samples of CC,
CS3, CG3 and CS3G3 specimens. The load amplitude applied to
the specimen is represented in terms of ‘Stress ratio’. The beams
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

Table 13
Results of Sulphuric Acid Attack Test on Selected Mixes.

Mixes Avg. Loss or gain in Weight (%) Compressive Strength (MPa)

0 Day 56 Day 90 Day 0 day 56 day 90 day
Conventional 0 1.633 2.916 59.67 50.16 41.3
CS3 0 1.167 1.913 70.33 61.33 55
CG3 0 1.243 2.083 68 57.67 53
CS3G3 0 0.847 1.345 77.33 66.33 58.67

Fig. 13. Cubes immersed in 5% magnesium sulphate for 56 & 90 days.

Table 14
Results of Sulphate Attack Test on Selected Mixes.

Mixes Avg. Loss or gain in Weight (%) Compressive Strength (MPa)

0 Day 56 Day 90 Day 0 day 56 day 90 day
Conventional 0 Not Significant +2.620 59.67 57.17 53
CS3 0 +1.343 70.33 66.67 64
CG3 0 +1.637 68 59.67 53.33
CS3G3 0 +1.153 77.33 72.5 70.5

Table 15
Fatigue life of selected best combination.

Stress ratio Criteria as per IRC:58-2015, minimum number of cycles No. of cycles to failure of the specimen
Conventional CG3 CS3 CS3G3
0.65 7700 >2,50,000 >2,50,000 >2,50,000 >2,50,000
0.7 1970 1,58,966 1,62,582 1,67,346 1,88,076
0.75 477 72,664 75,662 81,564 87,640
0.8 119 14,460 15,662 17,864 19,660
0.85 30 960 1116 1554 2004

are tested for stress ratios like 0.65, 0.7, 0.75, 0.8 and 0.85. The load
amplitude is maintained constant for a particular beam at the
given stress ratio. The fatigue life of all the best combinations
was shown in Table 15. The stress ratios are represented in increas-
ing order. From the table, at stress ratio 0.65, all the specimens can
take cycles greater than 2,50,000 numbers. As stress ratio
increases, the specimen takes a lesser number of cycles or it will
fail early. All the specimens tested to qualify the minimum criteria
given by the IRC: 58-2015 code, from which it takes more
number of cycles than the codebook prescribed for every stress
ratio [53].
The fatigue life i.e. the number of cycles for which concrete
beams fail is represented using graph called S-N curve in which
stress ratio ‘S’ is plotted on Y-axis and number of load cycles to fail-
ure ‘N’ on the X-axis (on a log scale) [54]. The S-N curves for the
test specimens were shown in Fig. 14. Table 16 shows the equa-
tions and R2 values for concrete specimens.
The results revealed that the concrete specimen CS3G3 can take
a greater number of cycles for a given stress ratio than all the spec-
imens tested. Thus the combined effect of SF and GO helps in filling
micro and nanopores between the inter transition zones. This
results in delayed formation and propagation of cracks under the

14
P.K. Akarsh, S. Marathe and Arun Kumar Bhat Construction and Building Materials xxx (xxxx) xxx

(a) Conventional Specimen (b) CS3 Specimen

(c) CG3 Specimen (d) CS3G3 Specimen

Fig. 14. Flexural Fatigue test results in-terms on S-N Curve.

Table 16  The flexural strength of CS3G3 specimen was 8.0 MPa which is
Relationship between fatigue cycle (N) and stress ratio (R). more than the minimum requirement for pavements. The per-
Mix ID Equations R2 value centage increase in early strength is more than the later stage
Conventional ln(N) = (1.044-SR)/0.03 0.9163 strength which is an advantage for the pavement application.
CS3 ln(N) = (1.076-SR)/0.03 0.9354  The similar type of stress to strain curves (Modulus of elasticity
CG3 ln(N) = (1.054-SR)/0.03 0.9305 values) are obtained for the best combination of concrete spec-
CS3G3 ln(N) = (1.090-SR)/0.03 0.9425 imens tested.
 The compressive and tensile strength of cylinder with CS3G3
mix shows greater resistance in compressive stresses and ten-
sile stresses than all the other combinations.
repeated loads. Whenever there is a lesser number of voids, the  Due to nano and micro filling of pores by Graphene oxide and
stresses can be easily distributed and more stresses can be resisted. silica fumes, the concrete specimens showed a lesser water
absorption and volume of permeable voids.
4. Conclusions and recommendations  From SEM analysis, the concrete containing both Silica fumes
and Graphene oxide shows dense hydration products than all
The specific conclusions from the current investigations are the other mixes. The GO in the presence of silica fume and PC
summarized below: based superplasticizer is well dispersed than GO in the presence
of PC based superplasticizer alone.
 The workability of the concrete containing both SF and GO  In XRD analysis, the high-intensity peaks were observed in the
shown a greater slump loss than other mixes. Since the specific CS3G3 specimen may be due to an increase in the hydration
surface area of both silica fumes and graphene oxide are less products; and there was a large number of peaks, which may
than the conventional cement, it consumes more water to wet due to improvements in the microstructure.
the surface of the material.  EDAX analysis shows the presence of Graphene oxide in con-
 The concrete with 0.15% GO and 7% silica fumes show 29.54% crete and e-ZAF quant results show improvements in the hydra-
increase in compressive strength than the conventional con- tion products may due to the combined effect of GO and silica
crete at 28 days. fumes.

15
P.K. Akarsh, S. Marathe and Arun Kumar Bhat
 The selected concrete mixes shown better resistance against
sulphate and acid attacks when compared with the conven-
tional concrete mix.
 The fatigue behaviour of concrete containing both SF and GO
shows greater resistance to the cyclic loads applied for a given
stress ratio or it can take a larger number of repetitive cycles
than other test specimens.
From the experimental investigations, it is proved that the
nanomodified concrete can be one of the solutions as a successful
pavement quality concrete for supporting heavy vehicle move-
ments since it satisfies the design requirements as per IRC
specifications.
In order to extract the complete potential of any nanomaterial,
then consideration should be given to dispersion property and
bonding between the cement hydration products. Formation of
agglomerates can create the voids. Hence, proper dispersion and
mixing techniques must be adopted. The use of it may reduce
the quantity of material required and the thickness of the slab.
Despite this, the use of nanomaterials as an additive in pavement
concrete can increase the material’s direct cost. Life cycle analysis
method must be used to evaluate the economic benefit of this
technology.
CRediT authorship contribution statement
P.K. Akarsh: Investigation, Visualization, Methodology, Formal
analysis. Shriram Marathe: Data curation, Writing - review & edit-
ing, Validation. Arun Kumar Bhat: Supervision, Resources,
Conceptualization.
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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