Reinforcing Effect of Graphene Oxide on Cement Paste

1. INTRODUCTION
The factors affecting the mechanical properties of concrete require level
investigations microstructure between the reactive paste (cement and water) and inert
aggregates (gravel and sand), concrete is a porous material composed of reactive material
and aggregates inert, is permeable to air and water properties and this has great influence
on the strength and durability of concrete structures, which traditionally has studied it from
this perspective, water to the concrete mix is added to increase workability and to facilitate
the process of hydration reaction of cement with water, more water more pores are formed
in the concrete, leading to reduction in strength and deterioration thereof, the mechanical
properties of concrete are determined by the porosity generated during the hydration
process the amount of water added to the mixture.

The graphene oxide is chemically conoicido as, atomically composite carbon, oxygen
and hydrogen, a three-dimensional structure composed of millions of layers of graphite;
existing in all body cast plain concrete or reinforced and which is possible to peel in the
water, creating highly resistant layers in the material in which you are dispersed.

Laboratory tests indicate that when mixtures of Portland cement are performed,
including controllably graphitic material agragados and steel reinforcement, the
mechanical properties, físiscas and concrete strength are improved to obtain the dispersion
of oxide layers graphene by the water used. There have been many investigations to
increase the strength of concrete by manipulating the properties of materials and quantities,
for example by adding minerals such as fly ash, silica fume, supplementary cementitious
materials, reinforcing clay particles and micro fibers. In recent years, research is moving
towards the nano reinforcement to generate high-strength concrete.

2. 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. The atomic
structure of Graphene is shown in figure 2.1.
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 Reinforcing Effect of Graphene Oxide on Cement Paste

Fig 2.1 Atomic structure of graphene

(Source: https://goo.gl/images/w3PO8U)
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. Graphene is the main element for the synthesis of all the other graphitic
materials of all dimensions. It can be found wrapped in zero-dimensional fullerenes, rolled
in one-dimensional nanotubes or stacked in three-dimensional graphite.

Graphene is a two-dimensional layer material and has one atom thickness, sp2covalent
bonded carbon atoms, which form a honey-comb crystal lattice. According to nano
indentation atomic force microscopy 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 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 inorder to facilitate its massive production and industrial
application.

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 Reinforcing Effect of Graphene Oxide on Cement Paste

3. GRAPHENE OXIDE
Graphene oxide is formed by a graphene layer with different functionalities oxygen,
mostly in the form of hydroxyl and epoxy groups, with small amounts of carboxyl,
carbonyl, occurs through chemical oxidation of graphite, with dispersion and exfoliation in
water or organic solvents, due to the stoichiometric composition of graphene oxide, their
amorphous character and the inhomogeneous distribution of the groups oxygen, atomic
precise structure is still unclear, in recent years have been proposed various models
structural.

In 1939, Hofmann and Holst proposed the first simple model of graphene oxide,
Reuss proposed a variation model of Hofmann and proposes the incorporation of hydroxyl
and ether oxygen, randomly distributed in the carbon structure Reuss in order to explain
the acidic properties of graphite oxide, reexamined structure incorporating hydroxyl and
carbonyl groups, Scholz and Boehm proposed a new structure with the carbon molecule
and carbonyl groups and hydroxyl, Nakajima et al. propose a model in which graphene
oxide has two carbon layers bonded together by carbon-carbon bonds, The best-known
model is the one proposed by Lerf and Klinowski with benzene rings unoxidized and
regions alicyclic hydroxyl bearing, Szabo et al. have proposed a new structural model
consisting of a network of carbon and two types of regions hexaloxide of grafenonos
planes with C = C bonds cyclohexane-trans linked and functional groups such as hydroxyl
compounds, ether, carbonyl and phenolics.

Graphite oxide was synthesized in 1859 by the British chemist B. C. Brodie. It was
investigating the graphite structure by observing the reactivity of graphite flakes. They
were carried out several reactions and one with addition of potassium chlorate to a
suspension of graphite low nitric acid. The material obtained is composed of carbon,
hydrogen and oxygen, oxidative treatments successive determined an additional increase in
the oxygen content, Staudenmaier developed an alternative process for the oxidation of
graphite it involves a mixture of sodium nitrate, achieving levels similar to those obtained
with the above method more economical oxidation.

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 Reinforcing Effect of Graphene Oxide on Cement Paste

Characterization of graphene oxide In order to study the structural characteristics of

graphene, they have been used various techniques where several authorised the distance
between layers of nanoplatelets to determine the characteristics of graphene oxide. Raman
spectroscopy becomes one of the most powerful techniques for graphene and related
materials is mainly used to observe the degree of order or disorder in the crystal structure

4. REINFORCING MECHANISM OF GRAPHENE OXIDE IN

CEMENTITIOUS MATERIALS
Till today, ordinary Portland cement 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. 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 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 percentage of hydration products are
calcium silicate hydrate 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: zero-
dimensinal-Fullerene, one-dimensional-Carbon nanotube, two-dimensinal-Graphene.
Figure 4.1 shows the different forms of carbon structure nano material.

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 Reinforcing Effect of Graphene Oxide on Cement Paste

Fig 4.1 Different forms of carbon structure nano material

(Source: https://goo.gl/images/yBXveR)
Of these, fullerene has not been suggested for reinforcement because of its low aspect
ratio. Compared to fullerene’s spherical shape, carbon nanotubes can be regarded as a one
dimensional tube thus having high-aspect-ratio. However, the incorporation of carbon
nanotubes in cement composites has proven to be rather complex and sometimes yields
contrasting results. Several researchers have found that the addition of carbon nanotubes
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 carbon nanotubes and
weak bonding between the carbon nanotubes 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 grapheme derivative,
graphene oxide consists of a monolayer of sp2-hybridized carbon atoms bearing many
oxygen containing functional groups on its surface, which render graphene oxide sheets

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 Reinforcing Effect of Graphene Oxide on Cement Paste

hydrophilic and highly dispersible in water. Planar structure of grapheme 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, forming a
nanocomposite. The two-dimensional 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. Nanoparticles show unique
physical and chemical properties due to their size, the nanoparticles have the ability to fill
the pores of the concrete structure allowing increased compressive strength.
The nano-silica particles and concrete with and without nanoparticles. It was
evaluated the compressive strength of concrete at 7, 14 and 28 days, samples with particles
noticing a high resistance to compression, this difference in resistance is caused by the
pozzolanic reaction with particles of nano-silica and evaluated higher amount of cement-
silica-water.

5. EFFECTS OF GO ON MECHANICAL PERFORMANCE

The addition of GO has a positive impact on the process of hydration, which can
directly transform into mechanical properties. To investigate the effectiveness of GO as
reinforcing material for cement composites, the aforementioned tests are conducted to
determine the compressive strengths and flexural strengths of both samples. It can be
concluded that the strengths of GO-cement composites outperform their plain-cement
counterparts encompassing all ages. This is due to the approximate degree of cement
hydration of both samples. At the age of 28 days, the GO-cement sample exhibits the
compressive strength of 71.42 Mega Pascal, increased by as much as 17.68 percentage.
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 Reinforcing Effect of Graphene Oxide on Cement Paste

The long-term enhancement in GO-cement sample can be explained by the

internal curing effect of GO. When the free water in cement matrix cannot meet the
continuous hydration, the absorbed water by GO surfaces will release gradually for
further hydration, which results in long-term enhancement. This reinforcing mechanism
of GO is called internal curing effect similar to rice husk ash. The flexural strengths of
GOcement composites are remarkably increased by 22.03 percentage and 22.55
percentage at 7 days and 28 days, respectively. The results suggest that GO nanosheets
exhibit significant toughening effects on cement composites. A hypothesis is put forward
that GO nanosheets play a vital role in the reduction of pre-flaws and refinement of cracks.

Except for the accelerated degree of hydration, the improvement of mechanical

strengths of GO-cement samples are highly dependent on the interfacial bonding between
GO and cement matrix. For traditional reinforcing materials, it is easy to cause them to
slide out of cement matrix due to the weak bonding, thus weakening the reinforcing
effects. As for GO, these interfacial bonding include both mechanical bonding and
chemical covalent bonding. The wrinkled edges and defect sites of GO sheets can act as
the interaction points with cement matrix to achieve stronger mechanical interlocking. The
covalent bonding provided by functional groups on GO surface corresponds to the case of
functionalized CNTs. These functional groups allow the development of strong interfacial
forces due to chemical reactions between carboxylic groups and hydration groups. The
high bonding strength between GO and cement matrix can improve the load transfer
efficiency and alleviate the stress concentration, as a result, mechanical strengths are
improved.

It is observed that the samples reinforced by GO nanosheets exhibit lower standard

deviations than plain-cement counterparts at all ages. The results highlight that the
uniformly dispersed GO nanosheets can improve the homogeneity of cement matrix, which
can facilitate to transfer the stress uniformly in case of stress concentration.

The agglomeration of GO nanosheets without modified by PC would badly degrade

the effectiveness of reinforcement. To confirm this hypothesis, we prepared new samples
containing 0.022 percentage GO and 0.22 percentage PC added to the mixer successively

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 Reinforcing Effect of Graphene Oxide on Cement Paste

without modification procedure. The mechanical strengths of these samples are decreased
in contrast with the plain-cement samples

This behaviour is justified by taking into account that GO without alternation by PC

tends to aggregate in alkaline pore solutions, pushing surrounding cement particles apart
and leaving large voids within cement matrix. Valid load-transfer in these weakness zones
is identified as the root cause for exacerbated mechanical performance.

6. EXPERIMENTAL STUDY

6.1 MATERIALS

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

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

6.1.1 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 (2grams) and NaNO3 (2grams) were mixed in 50 milliliter of
H2SO4 98 percentage in a 1000 milliliter volumetric flask kept under at ice bath
with continuous stirring.
2. The mixture was stirred for 2 hours at this temperature and potassium
permanganate (6 grams) was added to the suspension very slowly. The rate of
addition was carefully controlled to keep the reaction temperature lower than 15
degree celsius.
3. The ice bath was then removed, and the mixture was stirred until it became pasty
brownish and kept under stirring for 2 days.

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 Reinforcing Effect of Graphene Oxide on Cement Paste

4. It is then diluted with slow addition of 100 ml water. There action temperature was
rapidly increased with effervescence, and the color changed to brown color.
5. Further this solution was diluted by adding additional 200 milliliter of water stirred
continuously.
6. The solution is finally treated with 10 milliliter H2O2 to terminate there action by
appearance of yellow color.
7. For purification, the mixture was washed by rinsing and centrifugation with 10
percentage hydrochloric acid and then deionized water several times.
8. After filtration and drying under vacuum at room temperature, the graphene oxide
(GO) was obtained as a powder

Fig 6.1 Images of synthesized GO solution and powder

(Source: https://goo.gl/images/3G7B1P)

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 Reinforcing Effect of Graphene Oxide on Cement Paste

Fig 6.2 Synthesis of r-GO from graphite flakes

(source: https://goo.gl/images/SGE6bT)

6.1.2 Sample Preparation

Two mixes of cement paste with a water to cement ratio of 0.5 were prepared. One mix
was incorporated with 0.03 percentage 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] for 15 seconds
to homogenize the solution.
• Add cement powder within a period of 30 seconds while the mixer is operated at
the first preset speed for 60 seconds.
• Stop the mixer for 30 seconds, 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 for 30 seconds, stop the mixer for 15
seconds, and start the mixer at the same speed for an additional 30 seconds.

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 Reinforcing Effect of Graphene Oxide on Cement Paste

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

6.2 TESTING PROCEDURE

6.2.1 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 cement
salters 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.

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. Figure 6.3 shows the minislump flow for the plain cement
mixture with 0.03percentage by weight GO sheets.

Fig 6.3 Minislump flow at 10 minute after lifting up the minicore

(Source: https://goo.gl/images/U57M4m)
The minispread diameter of the plain cement sample is approximately 130 milimeter.
When 0.03 percentage by weight GO was added, it is observed that the diameter of
minislump is reduced to approximately 85 mm, which is 34.6 percentage lower than that of
the plain cement sample. The reduction of minislump diameter shows that GO additives

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 Reinforcing Effect of Graphene Oxide on Cement Paste

reduce the workability of cement paste. It is generally attributed to the large specific
surface area of nanomaterials that require more free water to wet their surfaces. The unique
two-dimensional 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. These separate studies infer an inverse correlation between
the concentration of GO and workability.
6.2.2 Compressive Strength
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. Figure 6.4 compares a typical compressive stress-strain curve of
plain cement specimen with that of the cement-GO composite.

Fig 6.4 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 43Megapascal. This value is

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 Reinforcing Effect of Graphene Oxide on Cement Paste

increased by as much as 46 percentage to approximately 63MegaPascal by having 0.03

percentage by weight GO sheets. Figure 6.5 compares the compressive strengths for plain
cement and GO cement samples at age 3, 7 and 28 days.

Fig 6.5 Compressive strengths for plain cement and GO-cement samples at ages of 3, 7,
and 28 days
6.2.3 Tensile Strength

Table 6.1 28th day tensile strength for both mixes

Mixes Tensile strength (MegaPascal)

Plain Cement 4.4 ± 0.3

GO-Cement 6.9 ± 0.4

Table 6.1 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 percentage 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.

7. ADVANTAGES
Among the fabrication methods of graphene, chemically oxidized graphene (Graphene
Oxide-GO) is widely used as starting material in favour 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

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 Reinforcing Effect of Graphene Oxide on Cement Paste

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.

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.

8. DISADVANTAGES
Despite of the remarkable reinforcing properties shown by grapheme oxide on cement
paste, it has a few limitations.

This include:

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 Reinforcing Effect of Graphene Oxide on Cement Paste

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

expensive due 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 water. Then reducing the availability of free water in cement paste.

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

9. APPLICATIONS

The main applications of Graphene oxide reinforced cement paste include;

• Precast products.
• Offshore and other structures in marine environment.
• Well cementing.
• Smart materials for structural health monitoring.

10. 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.

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 Reinforcing Effect of Graphene Oxide on Cement Paste

2. The use of GO increases the non-evaporable 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 percentage lower of total porosity,

27.7 percentage smaller amount of capillary pores, and more than 100 percentage
larger amount of gel pores than plain cement samples.

4. The refinement of pore structure could be caused by the enhancement in degree of

hydration.

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

REFERENCE

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Concrete (2015) ” International Journal of Engineering Science Invention
Research & Development , Vol. 1(Issue 8), Pg. 307-310.
[3] M Murugan, Manu Santhnam, “Influence of 2D rGO nanosheets on the properties
of OPC paste (2016)”, Cement and concrete composite Science direct, Vol.
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 Reinforcing Effect of Graphene Oxide on Cement Paste

[4] Nandhini S, Dr.Padmanaban, “Experimental Investigation On Graphene Oxide

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