160416L

GRAPHENE OXIDE MODIFIED CEMENT FOR STRUCTURAL

APPLICATIONS

T. I. Munmulla
University of Moratuwa, Bandaranayake Mawatha, Katubedda.
thisarimunmulla@gmail.com.
Prof. I. R. A. Weerasekera
University of Moratuwa, Bandaranayake Mawatha, Katubedda.

Abstract: The effect of cement modified with graphene oxide (GO) with its optimum dosage show
significant increase in mechanical, thermal and durability properties. However, the use of GO modified
cements is not promoted due to some inconsistent or contradictory results in the literature. It has found that
the carbon content in GO can influence the characteristics and properties of the GO and the corresponding
GO modified cement. The purity of graphite used for GO synthesis and modification will affect the carbon
content in GO. This paper has compared the effect of GO with different carbon content. The
study concludes that GO with high carbon content can improve the overall performance of
GO modified cement. Thus, it indicates that GO synthesized from a high-purity epigenetic
graphite deposit (lump/vein graphite) will show higher performance than the GO
synthesized from other graphite deposits.

Keywords: Graphene Oxide (GO); High purity graphite; GO modified cement; Lump/Vein
graphite

1.Introduction cement matrix, the filling effect. (Shah, Hou, &

Concrete which is a combination of cement,
aggregates and water is the most used material in
structural appliances which gives the strength and
durability to the structures. Nano modified
concretes and cement pastes can be used to achieve
advance properties in the structures.
Development of high performance cements with
developed mechanical and durability properties
such as better cement hydration, higher
compressive and tensile strengths, enhanced ability
to control cracking and shrinkage, ability to control
density, Development of sustainable concrete with
controlled energy dissipation and enhanced safety,
Development of cements with self-monitoring
ability are the main improvements that were able to
achieve with the nano modified cements. (de Brito
& Silvestre, 2015)
Seeding effect and filling effect are the major
mechanisms resulting the enhancement in
mechanical strength in nano modified cements.
Large surface area prevail in nano material will
provide nucleation sites for hydration products
which is the seeding effect. The nano size of the
materials makes them able to fill the pores in the
Konsta, 2015)
The main drawback in introducing the nano
modified cement in the practical application is
higher costs in production and difficulties in
dispersion due to strong Van der Waals forces
present.
Graphene Oxide (GO) is a strong oxidation product
of graphene contain oxygen functional groups. The
hydroxyl group (-OH), carbonyl group (-C=O) and
epoxy group (-CH(O)CH-) attached on the basal
plane, carboxyl group (-COOH) attached on the
edges (Yu, et al., 2016).
GO can be considered as a cost-effective material
when considering with other nano materials. The
oxygen functional groups in GO will facilitate the
dispersion in water and organic solvents and they
can improve interfacial bonding with the host
material due to chemical and physical interactions.
These properties have made GO a nanomaterial
which can be introduced in the practical
applications. (Jamal T. B., Tasnim, Pial, &
Rumman, 2016)
Addition of GO will increase the hydration,
mechanical and durability properties but will have
an adverse effect on workability. (Li, et al., 2017)

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Figure 1:Schematic reaction scheme between carboxylic acid groups and hydration productions [Ca(OH)2
and C–S–H] of cement. (Pan, et al., 2012)
and highly dispersible in water and it will enlarge
the interval between the layers. Alkalinity in the
2. Inconsistency of the Change in Properties of
mix can deoxygenate GO increasing the
GO modified cements
aggregation. (Li, et al., 2017)
Optimum dosage of GO is the key to improve the
It can be concluded that GO with higher number of
mechanical and durability properties of the
functional groups with lesser carbon content will
modified cements in required percentages. But the
have higher rate of dispersion.
optimum GO dosage and percentile increase in
properties varies from one literature to the another. 2.2 Workability of GO modified cements
Use of 0.04 and 1.00 wt% of GO in cement was A high flowability and moderate viscosity is
reported to increased compressive strength by 25% necessary to ensure the homogenous distribution of
and 47%, and flexural strength by 20% and 44%, engineering properties of concrete.
respectively, compared to plain cement paste at 28
Main drawback in GO modification in cement is
days. (Chen, Zhou, Wang, & Guo, 2018) Another
loss of workability. Workability decreases with the
study states that the compressive strength was
GO content. Study shows that addition of 0.05 wt%
increased by over 15.1% with 0.04 wt% GO at the
of GO will reduce workability by 42% when
same curing age. (Shang Y. , Zhang, Yang, Liu, &
compared with the plain cement. (Melbourne
Liu, 2015) Another with the 0.03 wt% of GO
Patent No. PCT/AU2012/001582, 2012)
discovers that the compressive was improved by
38.9% and flexural strength by 60.7%. (Lv, Ma, Low workability is generally associated with poor
Qiu, & Zhou, 2013) compaction capacity which may lead to non-
homogeneity due to entrapped large air voids that
According to the inconsistency in these results it
are retained in the composite. But, test results have
can be concluded that the properties of GO used
shown that there were no significant differences in
may affect the properties of the modified cements.
the entrapment of air voids between modified and
Therefore, study about the chemical composition of
normal cements. (Pan, et al., 2012)
GO and the resultant effect to the modified cement
is necessary. The hydrophilic functional groups and large surface
area of GO requires extra water to wet their
In this study the effect of carbon content in GO for
surfaces which reduces free water for lubrication.
the properties of cement paste is studied.
Better dispersed GO also will reduce workability
2.1 Dispersion of GO in Cement Matrix due to increased specific surface area. (Zheng,
Han, Cui, Yu, & Ou, 2017)
Aggregation of GO will result in the formation of
weak zones and it will obstruct the full utilization Therefore, it can be concluded that GO with higher
of GO. Therefore, it is recommended to use the carbon content with lesser functional groups and
suspension of GO rather than GO powder. specific surface area will not affect the workability
parameter of modified cements significantly.
Functional groups present in the GO sheets and
alkalinity of the cement paste will affect the GO 2.3 Mechanical properties
dispersion. Functional groups make GO hydrophilic

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According to literature it can be seen with the

addition of GO mechanical strengths of modified
cements increases. But with further increase in GO
will decrease the strength. Shang et al. discovered
that with the addition of 0.02, 0.04 and 0.06 wt% of
GO will increase flexural strength by 9.8%, 15.1%
and 12.4%. (Shang, Zhang, Yang, Liu, & Liu,
2015) Similar results were observed in other studies
also. This is due to aggregation of GO in the matrix
and overlapping of GO with each other due to high
concentration. (Saafi, Tang, Fung, Rahman, &
Liggat, 2015)
It is believed that GO will help to enhance the
packing density of calcium-silicate-hydrate (C-S-H)
gel and reduce the microstructure porosity to
strengthen the cement matrix. (Tong, et al., 2016)
It has reported that GO with better dispersibility
will result in higher mechanical strengths and also
smaller size of GO will enhance the strength
properties than the larger size GO. (Lv, Liu, Sun,
Ma, & Zhou, 2014)
Oxygen functional groups in GO have two main
functions, they provide heterogenous nucleation
sites for cement hydration and they act as a water
reservoir and generate water transporting channels.
This will accelerate the hydration of cement. Well-
disposed GO will be able to form a strong network
through cross-linking interactions by bridging the
edges of GO sheets, intercalating between the basal
planes and by cross-linking of the hydrogen bonds
formed among the oxygen functional groups and
water molecules. These processes will enhance the
mechanical properties of modified cements. (Zheng Figure 2:Morphology of GO with (a) 20% oxygen
content and (b) 33% oxygen content. Carbon,
Q. , Han, Cui, Yu, & Ou, 2017) oxygen, and hydrogen atoms are grey, red, and
It has also found that oxygen contentment in GO white, respectively (Zheng Q. , Han, Cui, Yu, & Ou,
2017)
affect the strength. It has mentioned with oxygen
content increasing from 12.36% to 25.45% the 2.4 Durability Properties
strength properties increased significantly, but with The durability of cement-based materials is the
further increase in strengths did not occur when the ability to resist corrosion and freezing and thawing
oxygen content increase 29.33%. (Lv S. , Ma, cycle. GO has the ability of reducing the total pore
Chaochao, & Zhou, 2013) area, median pore diameter, porosity and
But, it is also shown that structural defects of GO maintaining uniform pore diameter and it also has
increase with the increase of oxygen content the ability of hindering the initiation of microcracks
(Zheng Q. , Han, Cui, Yu, & Ou, 2017) as in which improve the transport properties. (Jamal T.
figure 02. B., Tasnim, Pial, & Rumman, 2016)
Therefore, it can be concluded that the active The surface of GO is capable of absorbing and
functional groups can not only promote the cement filtering chloride ions. (Sun, 2017) It is also shown
hydration and increase the strength properties but that with the addition of 0.01 wt% of GO chloride
also act as defects to reduce the strength properties. penetration depth decrease to 5 mm from 26 mm.
(Mohammed, Sanjayan, Duan, & Nazari, 2015)
It is important to identify optimum content of
oxygen functional groups or optimum carbon Although it has found that GO will improve the
content to obtain better results. durability properties, effect of carbon content or the
number of functional groups on that is not clear.

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3. Effect of graphene oxide produced from
epigenetic graphite deposit (Vein/ lump
graphite)
It can be observed that increase in carbon content
into its optimum level can enhance the properties of
GO modified cements.
The quality, Carbon content of GO depend on the
properties of parent graphite and the oxidation
method used. (Botas, et al., 2012)
In this section important qualities and suitable
parent graphite to obtain good quality GO is
discussed.
Naturally occurring graphite are found in three
different forms due to three different processes.
graphite deposit using Modified Hummers method
is 65.35 wt% and oxygen content is 34.05 wt%
which is higher than the percentages obtained by
using other graphite deposits. According to the
experimental results the rate of hydration
accelerated. GO dosage of 0.02 wt% increased
flexural strength by 83% and 0.04 wt% of GO
increased compressive strength by 26% compared
to the control mix without GO. 0.02 and 0.04 wt%
GO increased the electrical resistivity by 11.5% and
decrease the sorptivity by 29% which will improve
the mechanical and durability properties of the
modified cement. (Qureshi, Panesar, Sidhureddy,
Chen, & Wood, 2019)
4. Conclusion

1. Amorphous graphite Oxygen content or the number of functional

groups in GO will affect the performance of GO
2. Flake graphite and GO modified cements.
3. Vein/ Lump graphite Vein/lump graphite can be used to produce
Vein or lump graphite are extracted from epigenetic these GO with less oxygen content under
graphite deposits which produce the purest graphite relatively low expenses and in an
from all processes. Purity of vein graphite can be environmentally friendly process.
considered as more than 95.0% with graphite Further researches have to be carried out to
carbon content of more than 90.0% Cg even identify the micro-structure and the benefits of
without refining. It has higher thermal and using GO produced from vein/lump graphite for
electrical conductivity with highest degree of nano-modified cements.
cohesive integrity.
These epigenetic graphite deposits exhibit References
crystalline and rhombohedral stacking
(ABCABCA...) which is beneficial for the
fabrication of desirable graphene derivatives.
(Qureshi, Panesar, Sidhureddy, Chen, & Wood,
2019)
According to the experiments done by Botas, et al.
GO produced from more crystalline graphite
contain larger amount of epoxy groups and larger
surface area while GO produced from less
crystalline graphite contain larger proportion of
hydroxyl and carboxyl groups. (Botas, et al., 2012)
Although vein graphite has higher purity than other
forms of graphite, Through the synthesis of
artificial graphite or through chemically bonding
lower grades of graphite production of graphene
with over 99% of purity can be done. But the
material produced have inferior properties when
compared with natural crystalline vein graphite.
Chemical reduction of GO can also be used to
increase carbon content such as reduced graphene
oxide (rGO) but they are more expensive and
parent material has to undergo much more chemical
reactions which is not environmentally friendly.
Experiments done by Qureshi, et al. shown that
carbon content of GO extracted by epigenetic

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