INTRODUCTION

Patented in 1824 by Joseph Aspdin, a bricklayer and mason in Leeds, England,

ordinary portland cement (OPC) is the key ingredient of concrete, which is the world’s
most widely used building material. However it has limited structural applications without
the use of reinforcement due to poor tensile strength and strain capacity. The weak tensile
strength is associated with pre-existing flaws. By incorporating steel reinforcing bars and
fibres, it is possible to delay the development of microcracks and therefore improve
resistance to tensile stresses.

OPC paste is a brittle material characterized by a weak tensile strength because of

the presence of relatively large pores in the paste that may initiate macrocracks. Discrete
short fibers have been used to control cracking in fiber-reinforced concrete (FRC) to
improve its mechanical properties. The postcracking behavior of FRC depends on the
crack-bridging capability of the fibers. A wide variety of fibers has been used in the last
three decades, including steel, glass, carbon, and synthetic materials. These fibers, which
are usually randomly oriented in the concrete matrix, may not withstand the tensile
loadings as effectively as steel reinforcing bars, but they are more closely spaced and are
therefore better at controlling cracks. The efficiency of FRC highly depends on both the
mechanical properties and the geometry of the fibers employed.

Recent developments of novel nanosize fibers, such as carbon nanotubes (CNTs)

and graphene, have opened up new possibilities for improving the strength of cement paste.
Compared with traditional fibers, these nanoscale fibers can offer several distinct
advantages, namely, higher strength and stiffness, higher aspect ratio, and smaller fiber
spacing , that allow them to better prohibit or hinder the development of cracks at the
nanoscale level. Most studies on nanosize fibre-reinforced cementitious composite have
hitherto been focused on CNTs. Since the advent of graphene in 2004, graphene has raised
considerable attention as nanoscale reinforcement like CNTs. Graphene when oxidized
have a better dispersion in the matrix. The reinforcing effects of oxidized graphene sheets

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[generally termed as graphene oxide (GO)] on the mechanical properties of polymers can
be even better than those of CNTs.

GRAPHENE

Graphene is an allotrope of carbon in the form of a two-dimensional, atomic-scale,

honey-comb lattice in which one atom forms each vertex. It is the basic structural element
of other allotropes, including graphite, charcoal, carbon nanotubes and fullerenes. In simple
terms, graphene, is a thin layer of pure carbon; it is a single, tightly packed layer of carbon
atoms that are bonded together in a hexagonal honeycomb lattice.

Atomic structure of graphene

It is the thinnest compound known to man at one atom thick, the lightest material
known, the strongest compound discovered, the best conductor of heat at room temperature
and also the best conductor of electricity known. Graphene is highly inert and so can act as
a corrosion barrier between oxygen and water diffusion.

Carbon is the second most abundant mass within the human body and the fourth
most abundant element in the universe (by mass), after hydrogen, helium and oxygen. This
makes carbon the chemical basis for all known life on earth, so therefore graphene could
well be an ecologically friendly, sustainable solution for an almost limitless number of
applications.

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 Graphene is the main element for the synthesis of all the other graphitic materials
of all dimensions. It can be found wrapped in 0D fullerenes, rolled in 1D nanotubes or
stacked in 3D graphite.

Graphene is a 2D layer material and has one atom thickness, sp2 covalent bonded
carbon atoms, which form a honey-comb crystal lattice. The intrinsic strength of graphene
is 130 GPa and its Young’s modulus is 1 TPa according to nanoindentation atomic force
microscopy (AFM) for a single layer graphene sheet. Graphene’s planar structure is
beneficial for bondings on the upper and bottom surface in close distance with the hosting
material. The theoretical specific surface area of a single sheet of graphene could be 2630
m²/g, which is even higher than that of carbon nanotubes. The bigger the surface area is,
the more possible it becomes to interact physically and chemically with the host material
and enhance the bondings formed between these two materials. Although, graphene is
extremely attractive due to its remarkable properties, there is significant difficulty to
produce more than small quantities and lower the cost of production in order to facilitate
its massive production and industrial application.

GRAPHENE OXIDE

Although, graphene is extremely attractive due to its remarkable properties, there

is significant difficulty to produce more than small quantities and lower the cost of
production in order to facilitate its massive production and industrial application. For this
reason, Graphene Oxide (GO), which is a graphene derivative, has been examined as an
alternative nanomaterial to graphene.

While graphite is a 3 dimensional carbon based material made up of millions of

layers of graphene, graphite oxide is a little different. By the oxidation of graphite using
strong oxidizing agents, oxygenated functionalities are introduced in the graphite structure
which not only expand the layer separation, but also makes the material hydrophilic
(meaning that they can be dispersed in water). This property enables the graphite oxide to
be exfoliated in water using sonication, ultimately producing single or few layer graphene,

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known as graphene oxide (GO). The main difference between graphite oxide and graphene
oxide is, thus, the number of layers. While graphite oxide is a multilayer system, in a
graphene oxide dispersion, a few layers flakes and monolayer flakes can be found.
Graphene Oxide is also a single layer material of sp2 hybridized carbon atoms derivatized
by a mixture of hydroxyl and epoxy functional groups.

Synthesis of r-GO

One of the advantages of the gaphene oxide is its easy dispersability in water and
other organic solvents, as well as in different matrixes, due to the presence of the oxygen
functionalities. This remains as a very important property when mixing the material with
ceramic or polymer matrixes when trying to improve their electrical and mechanical
properties.

REINFORCING MECHANISM OF GRAPHENE OXIDE IN CEMENTITIOUS

MATERIALS

Till today, ordinary Portland cement (OPC) retains its popularity as construction
material in the field of civil engineering. However, the major disadvantage of cement based
material is its brittle nature which is attributed to its poor resistance to crack formation and
propagation.

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 Many attempts have been carried out to improve the performance of cement
composites by addition of reinforcements such as microfibers. It has been demonstrated
that fiber reinforced-cements (FRC) strengthen and toughen the brittle cement composites
by controlling the cracks either at micro-level or macro-level. However, the addition of
microfibers does not alter the loosely stacked cement hydrates, so they fail to arrest cracks
originated at nanoscale. If nano-cracks can be successfully controlled, their propagation to
micro-level is likely to be prevented. Since 70% of hydration products are calcium silicate
hydrate (C-S-H) gels at nanoscale, it is deduced that nano-reinforcements are more
effective than conventional fibers because they can control nano-cracks existing at the
initial stage.

In recent years, there has been increasing research conducted on the incorporation
of nano-scale smart materials in cementitious composites. These smart materials are
alternative materials such as nanoparticles and nanofibers which enhance certain properties
of the cementitious composite, such as durability and strength by decreasing permeability
and inhibiting nano-cracks in a material. Of these nanomaterials, carbon structure
nanoparticles have been gaining attention as a possible material used to reinforce
cementitous composites. Carbon structure nano materials are of different types: 0 D-
Fulllerene, 1 D- Carbon nanotube, 2 D-Graphene.

Different forms of carbon structure nano material

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 Of these, fullerene has not been suggested for reinforcement because of its low
aspect ratio. Compared to fullerene’s spherical shape, carbon nanotubes (CNTs) can be
regarded as a one dimensional tube thus having high-aspect-ratio. . However, the
incorporation of CNTs in cement composites has proven to be rather complex and
sometimes yields contrasting results. Several researchers have found that the addition of
CNTs results in little change in strength or even a deterioration of the composite in some
cases. The reasons for this are generally attributed to the poor dispersion of CNTs and weak
bonding between the CNTs and the cement matrix.

Recently, graphene has attracted great interests due to its unique mechanical,
electrical and thermal properties and excellent performance as the polymeric reinforcing
material. Nano-particles with large surface areas can be exploited as nucleation sites for
cement hydrates as well as pore fillers for dense microstructure. As a graphene derivative,
graphene oxide (GO) consists of a monolayer of sp2-hybridized carbon atoms bearing
many oxygen containing functional groups on its surface, which render GO sheets
hydrophilic and highly dispersible in water. Planar structure of graphene sheets which
creates significant contact area with the cement material. Mechanical properties and shape
of graphene oxide are the main reason of significant improvements in compressive and
flexural strength of the cement materials. The superlative properties of graphene oxide has
a promising future when combined with ordinary Portland cement (OPC), forming a
nanocomposite. The 2D GO nanosheets provide an extra dimension to interact with cement
and concrete matrix. The negatively charged GO sheets interact with the ions in cement
paste by electrostatic interactions, leading to formation of agglomerates. With the
concurrent benefit of excellent mechanical performance, graphene will improve the
toughness and strength of cementitious matrix materials. The hydration of cement and the
accompanying phenomena such as heat generation, strength development and shrinkage
are the results of interrelated chemical, physical and mechanical processes. All these
processes of hydration kinetics play an important role on microstructural development and
final properties of hydrated cement pastes.

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EXPERIMENTAL STUDY

1 Materials

I. GO sheets were synthesized from natural graphite by using a modified Hummer’s

method, which mainly involves chemical oxidation of the graphite powder.

1.1 Modified Hummer’s method of synthesis

The most common method of synthesis is chemical method of synthesis by

Modified Hummer’s method. This method of synthesis can be varied by varying the
oxidizing agents used to exfoliate graphite flakes.

Chemicals required:
Graphite Flakes, Sodium nitrate, Potassium permanganate, Hydrogen peroxide,
Sulphuric acid, Hydrochloric acid.

The stepwise preparation is given as follows:

1. Graphite flakes (2g) and NaNO3 (2g) were mixed in 50 mL of H2SO4 (98%) in a 1000mL
volumetric flask kept under at ice bath (0-5°C) with continuous stirring.
2. The mixture was stirred for 2 hrs at this temperature and potassium permanganate (6 g)
was added to the suspension very slowly. The rate of addition was carefully controlled to
keep the reaction temperature lower than 15°C.
3. The ice bath was then removed, and the mixture was stirred at 35°C until it became pasty
brownish and kept under stirring for 2 days.
4. It is then diluted with slow addition of 100 ml water. The reaction temperature was
rapidly increased to 98°C with effervescence, and the color changed to brown color.
5. Further this solution was diluted by adding additional 200 ml of water stirred
continuously.

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6. The solution is finally treated with 10 ml H2O2 to terminate the reaction by appearance
of yellow color.
7. For purification, the mixture was washed by rinsing and centrifugation with 10% HCl
and then deionized (DI) water several times.
8. After filtration and drying under vacuum at room temperature, the graphene oxide (GO)
was obtained as a powder.

Images of synthesized GO solution and powder

Synthesis of r-GO from graphite flakes

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1.2 Sample Preparation:

Two mixes of cement paste with a water to cement ratio (w/c) of 0.5 were prepared.
One mix was incorporated with 0.03% by weight GO sheets by the weight of cement. The
other was a plain cement mix that serves as the reference sample. A high-speed shear mixer
was employed for the mixing to improve the distribution of GO sheets in the matrix.
Mixing procedures similar to ASTM C1738-11a were adopted:

• Add the correct amount of GO solution and water to the mixing container and premix the
solution at low speed [100–200 revolutions per minute (rpm)] for 15 s to homogenize the
solution;
• Add cement powder within a period of 30 s while the mixer is operated at the first preset
speed (4,000 rpm) for 60 s;
• Stop the mixer for 30 s, during which any paste that may have collected on the sides of
the bowl is scraped down into the hatch; and
• Operate the mixer at the second preset speed (12,000 rpm) for 30 s, stop the mixer for 15
s, and start the mixer at the same speed for an additional 30 s.

After mixing, a portion of the mixture was used for the minislump test, while the
rest of the mixture was cast into molds and vibrated on a vibration table to ensure a good
compaction. The molds were then sealed with polyethylene sheets to prevent the escape of
moisture. After 24 h, the samples were de-molded and cured in a lime-saturated water bath
at 20°C.

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2 Testing Procedure

2.1 Workability

Workability is a key parameter to gauge the ease of transport and placement of fresh
concrete. Regardless of the microfibre type, the loss of workability is proportional to the
concentration of fibre in concrete. Worse still, the inclusion of nanomaterials in cements
alters the rheological properties of pastes and severely degrades the workability of mortars
and concrete mixtures. The large surface area of nanomaterials demands more water to wet
their surface, thereby reducing the free water content required for lubrication at a given
water-to-cement ratio (w/c).

To evaluate the influence of GO sheets on the workability of the cement paste mini
slump test was performed. Immediately after mixing, mixtures were poured into a minicore
to perform the minislump test.

Minislump flow at 10 minute after lifting up the minicore

Fig.6 shows the minislump flow for the plain cement mixture with 0.03% by
weight GO sheets. The minispread diameter of the plain cement sample is approximately
130 mm. When 0.03% by weight GO was added, it is observed that the diameter of
minislump is reduced to approximately 85 mm, which is 34.6% lower than that of the
plain cement sample. The reduction of minislump diameter shows that GO additives
reduce the workability of cement paste. It is generally attributed to the large specific

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surface area of nanomaterials that require more free water to wet their surfaces.

The unique 2D GO sheet being a double-edged sword, promotes C–S–H nucleation

at the expense of a lower workability. The hydrophilic GO has a large surface area to adsorb
water molecules present in the mix to its surface. As a result of the lack of free water, the
frictional resistance among the cement particles and the sheets is increased without ample
lubrication. This inter-particle friction phenomenon has been identified as the root cause
for exacerbated workability. Moreover, it is emphasized that small amounts of GO sheets
(0.02–0.05 wt.%) exhibits an even poorer workability than CNTs. These separate studies
infer an inverse correlation between the concentration of GO and workability. Despite the
excellent dispersion of GO nanosheets in the cement matrix, poly-carboxylate remains an
indispensable admixture for reducing water consumption without losing the fluidity of the
cement paste.

2.2 Hydration

The TGA (Thermo Gravimetric Analysis) test results of the nonevaporable water
content and the calcium hydroxide content at ages of 3, 7, and 28 days are presented. As
expected, both the non-evaporable water content and the calcium hydroxide content in the
plain cement samples increase with the age of hydration. It is observed that the non-
evaporable water content and the calcium hydroxide content in the GO-cement samples
follow a similar increasing trend as those in the plain cement samples, but they exhibit
consistently higher proportions than those in the plain cement sample at all the test ages.

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(a) Nonevaporable water content (b) calcium hydroxide content in plain cement samples
and GO-cement samples at different ages

At the age of 28 days, the non-evaporable water content and the calcium hydroxide
content in the plain cement samples are 14.7 and 20.5%, respectively. With the addition of
0.03% by weight GO, these values are increased by 9 and 6%, respectively. Because both
the non-evaporable water content and calcium hydroxide content are considered as reliable
measurements of the degree of hydration, these results suggest that the addition of GO
sheets enhances the degree of hydration of the cement paste at different ages. It has been
reported that the addition of GO can increase the degree of crystallinity in polymeric
nanocomposite by providing preferential nucleation sites. Given that cement hydration
process is mainly controlled by the nucleation and growth of hydration products, the
enhanced degree of hydration in GO-cement composites could also be caused by the
nucleation effects of GO.

2.3 Porosity and Pore size distribution

The results of porosity test for the plain cement samples and the GO-cement
samples after 28-day curing are shown.

Table Porosity, Average Pore Diameter, and Total Pore of the Two Mixes at 28 Days
Total Gel Pore Capillary Pore Average pore Total pore
Mixes Porosity (%) (<10nm)(mL/g)3 (10nm-10µm) diameter Area
(mL/g)3 (nm) (m2/g)

Plain Cement 32.8±0.2 0.022 ± 0.002 0.173 ± 0.003 21.3 ± 1.1 39.7 ± 0.8

GO-Cement 28.2 ± 0.7 0.046 ± 0.002 0.125 ± 0.004 13.5 ± 0.2 54.0 ± 1.0

It was observed that the use of GO decreases the total porosity of cement paste.
With 0.03% by weight GO, the GO-cement composite has a total porosity of 28.2%, which

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is 13.5% lower than that of its plain cement counterpart. The decrease of porosity could be
caused by the improved degree of hydration in the GO-cement samples as shown by the
TGA results. It was also observed that the amount of capillary pores (10 nm< d < 10 μm)
in the GO-cement samples is 0.173 mL/g, which is 27.7% lower than that of the plain
cement. However, the amount of gel pores (d<10 nm) in the GO-cement sample was found
to be more than 100% higher than that of the plain cement. The distributions of pore sizes
for both samples can be illustrated using a log differential intrusion curve as shown.

Pore size distribution for plain cement paste and GO-cement composite

It was observed that the amount of mercury intruded to pores with d < 10 nm is
consistently higher in the GO cement sample, whereas the intrusion to pores with d > 10
nm is consistently lower in the GO-cement sample. These results show that the presence
of GO refines the pore structure of cement paste. Also, the doubling of gel pore volume in
the GO-cement samples indicates that more calcium-silicate-hydrate gel may have formed
in the GO-cement composite than in the plain cement sample. The refinement of pore
structure is further confirmed by the results of average pore diameter which show that the
mean pore diameter of the GO-cement sample is 36.7% finer than that of the plain cement
paste. Furthermore, the measurement of specific pore surface area shows that the addition
of 0.03% by weight GO increases the total pore area in cement paste by approximately

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36%, from 39.7 to 54 m²/g. This increase may be attributed to the refinement of pore
structure and particularly the significant increase of gel porosity in the GO-cement samples.

2.4 Compressive Strength

Fig.9 compares a typical compressive stress-strain curve of plain cement specimen

with that of the cement-GO composite. It is observed that the use of GO increases not only
the failure stress but also the failure strain. The influence of GO on failure stress and strain
of cement paste is similar to that of carbon nanotubes.

Typical stress-strain curves for plain cement paste and GO-cement sample

The compressive strengths of cement samples reinforced with GO sheets at

different ages are compared with those of plain cement paste. It was observed that the
compressive strengths of both mixes increase with respect to the ages of the samples as
expected. The results show that samples reinforced with GO exhibit consistently a higher
compressive strength than the plain cement samples at all test ages. At the age of 28 days,
the compressive strength of the plain cement sample is 43 MPa. This value is increased by
as much as 46% to approximately 63 MPa by having 0.03% by weight GO sheets.

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 Compressive strengths for plain cement and GO-cement samples at ages of 3, 7, and 28
days

2.5 Tensile Strength

Table shows the 28-day tensile strength results obtained from the tensile splitting
tests. It was observed that the tensile strength of the samples reinforced with GO is
approximately 50% higher than that of the plain cement sample. The strength gain could
be contributed by refinement of pore structure that arises from increase of the degree of
hydration.

Table 28th day tensile strength for both mixes

Mixes Tensile strength (MPa)

Plain Cement 4.4 ± 0.3

GO-Cement 6.9 ± 0.4

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ADVANTAGES OF USING GO

Among the fabrication methods of graphene, chemically oxidized graphene (Graphene

Oxide-GO) is widely used as starting material in favor of its good dispersion, bulk
production and unique multifunction properties. The graphene nanoparticles are expected
to improve the cement matrix in a nanoscale and therefore its microscale structure. The
little quantity of graphene could improve or even replace the traditional reinforcement and
also improve the mechanical properties of cement. Because of the high specific surface
area and aspect ratio of the GO, a small amount of the material is sufficient to enhance the
mechanical properties.

1. GO can regulate the shape and assembly of hydration products and control cracks
initiation and propagation at nanoscale.

2. Introduced graphene nanoparticles in the cement paste showed that this change in
microstructure improved its thermal and electrical diffusivity, which means that
micro-cracks due to the exothermic hydration process can be avoided.

3. The presence of GO increased amount of C-S-H gel at the cement nanocomposite

compared with pure cement mortar.

4. It shows high early age strength and long term durability.

5. It could prolong the civil structures’ service life significantly, thus reduce the
cement’s production needed and the air pollution of the construction industries.

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 6. Graphene could possibly integrate into the cement paste or mortar and strengthen
the bonds of the cement hydrates. As a result, the fundamental properties of cement
and especially its tensile and compressive strength could be improved.

DISADVANTAGES

Despite of the remarkable reinforcing properties shown by grapheme oxide on

cement paste, it has a few limitations. This include:

1. The use of graphene oxide in reinforcing cementitous materials is found to be

expensivedue to the high cost of production of the graphene oxide and thus
found to be very uneconomical to produce them in large scale.
Thus the major concern is to develop cheaper and more economical synthesis of graphene
oxide, which will allow for the use of graphene oxide on an industrial scale.

2. The workability of GO-cement also shows a small reduction. This is due to

the large surface area of grapheme oxide, which results in adsorption of a
large amount of watter. Thue reducing the availability of free water in cement
paste.

This can be resolved by the use of super plasticizers. The plasticizers improves fluidity
andthus the workability.

APPLICATIONS

The main applications of Graphene oxide reinforced cement paste include;

• Precast products.
• Offshore and other structures in marine environment.
• Well cementing.

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 • Smart materials for structural health monitoring.

CONCLUSION

Incorporation of graphene nanoparticles in cement paste showed interesting

modifications in the strength, hydration and also in the microstructure of the cement paste.
The dispersion and contact of the GNP and geopolymer matrix are the major factors
influencing the mechanical enhancement mechanism. The graphene oxide embedded to the
cement matrix is expected to improve cement’s toughness and more specifically its tensile,
compressive, or bending and interfacial strength. . It is expected to have great progress
towards this direction in the future.

From experimental results the influence of 0.03% by weight GO (by weight of

cement) on the workability, degree of hydration, pore structures, and strength of the OPC
paste can be summarized as follows:

1. The addition of a small proportion of GO sheets reduces the workability of OPC.

2. The use of GO increases the nonevaporable water content and calcium hydroxide content
in OPC paste at different test ages. The results indicate that the degree of hydration of OPC
paste
is enhanced by GO.

3. Cement samples containing GO exhibit 13.5% lower of total porosity, 27.7% smaller
amount of capillary pores, and more than 100% larger amount of gel pores than plain
cement samples.
The refinement of pore structure could be caused by the enhancement in degree of
hydration.

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4. The addition of GO enhances the strength of OPC paste. The 28-day compressive
strength and tensile strength are increased by over 40% with 0.03% by weight GO.

REFERENCES

[1] Li Zhao, Xinli Guo (2016),” Investigation of the effectiveness of PC@GO on the
reinforcement for cement composites”, Construction and Building Materials
Sciencedirect, Vol. 113, Pg. 470-478

[2] M Murugan, Manu Santhnam (2016),” Influence of 2D rGO nanosheets on the

properties of OPC paste”, Cement and concrete composite Sciencedirect, Vol. 70, Pg.48-
59

[3] Nandhini S, Dr Padmanaban (2016),” Experimental Investigation On Graphene Oxide

Composites With Fly Ash Concrete”, International Journal of Modern Trends in
Engineering and Science, Vol. 3, Issue 8, Pg. 176-179.

[4] Valles Romero Jose Antonio, Cuaya Simbro German (2016),”Optimizing content
graphene oxide in high strength concrete”, International Journal of scientific research and
management (IJSRM), Vol. 4, Issue 6, Pg. 4324-4332.

[5] Wang M, Wang R, Yao H (2016), "Adsorption characteristics of graphene oxide

nanosheets on cement." RSC Adv.

[6] M. Devasena, J. Karthikeyan (2015),”Investigation On Strength Properties Of

Graphene Oxide Concrete”, International Journal of Engineering Science Invention
Research & Development, Vol. 1, Issue 8, Pg. 307-310.

19
[6] Ahmadreza Sedaghat, Manoj K. Ram (2014),”Investigation of Physical Properties of
Graphene-Cement Composite for Structural Applications”, Open Journal of Composite
Materials, Vol. 4, Pg. 12-21.

[7] Frank Collins, Gong (2014),” Reinforcing Effects of Graphene Oxide on Portland
Cement Paste”, Journal of Materials in Civil Engineering ASCE library, Vol. 27, No. 2

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