Journal of Alloys and Compounds 698 (2017) 807e813

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Graphene oxide-reinforced aluminum alloy matrix composite

materials fabricated by powder metallurgy
Hansang Kwon a, *, Jayanta Mondal b, Khaled AloGab c, Va€ino Sammelselg b,
Miyazaki Takamichi d, Akira Kawaski d, Marc Leparoux e, **
a
Department of Materials System Engineering, Pukyong National University, Sinseonro 365, Namgu, 608-739, Busan, Republic of Korea
b
Institute of Physics, University of Tartu, Ravila 12c, Tartu, 50411, Estonia
c
National Centers for Advanced Materials, KACST, PO Box 6086, Riyadh, 11442, Saudi Arabia
d
Department of Materials Processing Engineering, Graduate School of Engineering, Tohoku University, Sendai, 980-8579, Japan
e
Laboratory of Advanced Materials Processing, EMPA-Swiss Federal Laboratories for Materials Science and Technology, Feuerwerkerstrasse 39, 3602, Thun,
Switzerland

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

Article history: Graphene oxide (GO) powder was dispersed in an AlMg5 matrix using high energy ball milling. The
Received 20 June 2016 obtained blend was then completely densified by hot pressing. No further hardening processing step was
Received in revised form performed. Nevertheless, only 1 vol% of GO in the Aluminum alloy matrix leads to a significant
9 December 2016
improvement of the mechanical resistance. The ultimate tensile strength (540 MPa) and the macro
Accepted 15 December 2016
Available online 24 December 2016
hardness (166 HV) are increased by a factor of 2 compared to the same AlMg5 alloy without nano-
particulate material and compacted under the same conditions. The bending strength is even increased
by a factor of 4 reaching a value over 800 MPa. The GO powder can be applied as a mechanical rein-
Keywords:
Aluminum-magnesium5 (AlMg5)
forcement to other scenarios such as polymer and ceramic systems.
Graphene oxide (GO) © 2016 Elsevier B.V. All rights reserved.
Hot-pressing
Tensile strength
Flexural strength
Powder metallurgy

1. Introduction interested in graphene oxide- (GO-) reinforced composite mate-

Superlight materials with high mechanical strengths are always
in demand in many industrial fields, especially those that produce
transportation machines, such as automobiles, trains, ships, and
aviation technologies. Carbon nanotubes [1] and graphene [2],
which are both carbon allotropes, are strong candidates for high
performance next generation structural materials because of their
chemical stabilities and good mechanical, electrical, and thermal
properties. However, because of their very fine sizes and shapes,
strong chemical interactions, and lack of suitable dispersion and
fabrication methods, such nanomaterials are relatively difficult to
handle and embed into metal matrix composite systems [3e5].
Recently, numerous researchers and scientists have become
* Corresponding author.
** Corresponding author.
E-mail addresses: kwon13@pknu.ac.kr (H. Kwon), marc.leparoux@empa.ch
(M. Leparoux).
rials, which are relatively cheap and easy to mass produce [6e8].
Graphene oxide was first prepared in 1859 by Brodie [9], who
treated graphitic powder with a mixture of potassium chlorate in
concentrated fuming nitric acid. In the subsequent years, graphene
oxide was mainly used as an expanded graphite intermediate;
however, the discovery of graphene resulted in enormous interest
in graphite oxide, itself [10]. GO is composed of single layers of
graphene with O, OH, and COOH groups attached to it, while
graphite oxide is composed of layers of GO that are partly preser-
ving the graphitic bonds between the layers [11]. However, one of
the advantages of GO is its dispersability in water, other solvents,
and different matrixes, due to the presence of the oxygen consisting
functionality radicals [12]. GO could, therefore, be used for
dispersion strengthening of materials. Recently, some studies
related to GO-reinforced composite materials have been reported.
Studies have been mainly focused on reduced graphene oxide
(RGO) reinforced metal matrix composites. However, studies on
graphene oxide (GO) reinforced metal matrix composites are rela-
tively limited at present [13e16].

http://dx.doi.org/10.1016/j.jallcom.2016.12.179
0925-8388/© 2016 Elsevier B.V. All rights reserved.
808 H. Kwon et al. / Journal of Alloys and Compounds 698 (2017) 807e813
In this study, we have fabricated and characterized GO-
reinforced Al alloy matrix composite materials without any pre-
liminary graphene oxide reduction process. Mechanical properties,
such as tensile strength, elongation, and deflection flexural
strength of the composites were measured and are discussed. The
microstructures of the composites were also observed in order to
interpret the mechanical properties.
2. Experimental procedure
Gas-atomized aluminum-magnesium5 (AlMg5) alloy powder
(ECKA Granules, purity 99.5%, particle size < 63 mm) and self-
prepared graphene oxide (GO) powder (5e20 nm thickness and
~1 mm in length), were used as matrix and reinforcement materials,
respectively. The GO powder was synthesized at the University of
Tartu from graphite powder (Strem Chemicals) using the modified
Hummers method [17] followed by drying out the GO water-
immersion in air at room-temperature. The AlMg5 powder and
the GO particles were mixed in a planetary ball mill (Retsch GmbH,
PM400) for 20 h, in an argon atmosphere, at 360 rpm, using Ø10-
mm balls with a 10:1 ball-to-powder weight ratio. As process
control agent 20 wt% heptane was used. Blends with a composition
of AlMg5-1 vol% GO were prepared. The milling vessels containing
the blends were transferred to a glove-box with a controlled inert
argon atmosphere before opening. The milled powder was
passivated for almost one week because the freshly milled powder
was in a highly activated energy state and could have easily
oxidized/burned upon contact with air. After passivation, the
composite powder was placed in a high-temperature steel mold.
The mold was then heated in air to the desired pressing tempera-
ture, 550
C, for 1.5 h and transferred rapidly (less than 5 s) to a
uniaxial press (Walter þ Bai AG, Switzerland). A pressure of
570 MPa was then applied to the composite powder for 4 s. The
resulting samples had a 30 mm diameter and were approximately
5 mm in thickness.
The densities of the composites were measured based on the
Archimedes' method, according to ISO 3369:1975. The micro-
structures of the chemically etched (30% NaOH) composites and
fracture surfaces were observed by high resolution cold field
emission scanning electron microscopy (Hitachi, FE-SEM S-4800),
energy-dispersive spectroscopy (EDS), and high-resolution
Fig. 1. (aec) SEM micrographs of raw AlMg5 alloy powder particles, (d and e) raw graphene oxide (GO), and (f) TEM image of graphene oxide.
transmission electron microscopy (HR-TEM, Hitachi, Japan). A
Zwick ZHU 2.5 Martens hardness tester was used to obtain
indentation modulus (EIT) and Vickers hardness (HV10) values ac-
cording to standard EN-ISO 14577:2003 [18]. A loading speed of
0.2 mm/min, an unloading speed of 0.1 mm/min, a maximum load
of 100 N, and a dwell time of 15 s were used. At least five mea-
surements were performed on each material. Tensile tests were
performed using flat dog bone samples with thicknesses of 3.0 mm
and Lo values of 10 mm, in accordance to EN-ISO 6892-1:2010 [19].
The tests were carried out using position control and a strain rate of
3  103 1/s, in a universal testing machine (Walter þ Bai AG,
Switzerland). At least four specimens were tested per sample. Four-
point bend tests were performed using a 150 kN servo-hydraulic
test machine (Walter þ Bai and DionSTAT software). Sample di-
mensions were approximately 3  5  22 mm. The test fixture
upper span length (Li) was 6.5 mm and the lower span length (L)
was 19.5 mm (span ratio 1/3). Testing was carried out using posi-
tion control and a constant speed of 1 mm/min. XRD patterns were
measured with an X'Pert Pro diffractometer (PANAlytical) with a
Cu-Ka radiation source (l ¼ 1.54056 Å, 45 kV and 40 mA) and a
linear detector (X'Celerator), in a 2q range of 20e80
. A step size of
0.0167
and a scan rate of 0.05
/sec were used. Grain sizes and
lattice strain were calculated from these patterns using the Scherrer
equation [20]. Raman spectroscopy was performed using a red He-
Ne ion laser with a wavelength of 633 nm (Leica) to evaluate dis-
order in the graphene oxide structure.
3. Results and discussion
Irregularly shaped, raw, polycrystalline AlMg5 particles of
various sizes (from approximately 100 nm to several micrometers
in diameter) are shown in Fig. 1 (aec). The raw graphite oxide (GO)
particles were settled from the water suspension. As no additional
functionalization of the GO nanosheets was done the sheets tend to
coagulate into a stacked multilayer state as shown in Fig. 1def and
they were not individually separated. The morphologies of the
high-energy ball milled AlMg5-1vol% GO particles (Fig. 2a) were
more spherical that those of the raw AlMg5 particles (Fig. 1a).
After milling, the size distribution of the blend particles be-
comes broader with particles from approximately ten to hundred
micrometers in diameter, however the shape is less angular as in
 H. Kwon et al. / Journal of Alloys and Compounds 698 (2017) 807e813
Fig. 2. (a) SEM micrographs of high-energy ball milled AlMg5-1vol% GO composite particles and (b and c) higher resolution images of those particles.
Table 1
Grain sizes and lattice strains of hot-pressed samples of pure AlMg5 and GO-reinforced AlMg5 matrix composites.
Sample Density (g/cm3) Hardness HV10 ± 2.3
Al5Mg bulk material 2.64 (100) 70
Al5Mg-1vol%GO composite 2.64 (100) 66
the raw Al-alloy powder. In general, grain growth occurs easily
during ball milling by cold-welding [21]. However, the particles
obtained by milling not only showed grain growth by cold-welding,
they also showed grain growth due to agglomeration of fine par-
ticles generated during the high-energy ball milling process. Ag-
glomerations of very fine particles are shown for instance in Fig. 2b
and c, and have been observed in all composite powders. The
milling parameters used seem to result in an efficient energy
transfer from the balls to the powders through the heptane process
control agent. It was difficult to observe GO particles in the blends
by electron microscopy meaning that they were trapped in the soft
AlMg5 particles and/or well dispersed throughout the AlMg5
matrix.
The hot-pressed (HPed) AlMg5-1 vol% GO composites were fully
densified, as indicated in Table 1. Fully dense pure AlMg5 bulk
material samples, fabricated using the same parameters, were
prepared for comparison (Table 1).
Fig. 3 shows XRD patterns of the raw materials, AlMg5-1vol% GO
powder, and HPed composite. It is difficult to detect light elements
by ordinary XRD because of their low electron densities. As a result,
Fig. 3. XRD patterns of the GO powder, the pure AlMg5, the AlMg5e1vol%GO powder,
and the AlMg5e1vol%GO composite.
809
Indentations modulus (GPa) ± 1.5 Grain size [nm] ± 10% Lattice strain [%] ±0.05
53 187 0.158
73 92.3 0.095
the GO powder shows a very low peak intensity [22]. The XRD
patterns of the raw AlMg5 powder, AlMg5-1vol% GO power, and the
HPed composite are similar. No secondary phase was observed in
the patterns, even though the composite was fabricated at 550
C.
In general, Al can easily react with carbon to form carbides. How-
ever, we could not detect any carbide phase because of the
following two reasons. Firstly, we believe that no residual carbon
was present in the raw GO powder. And secondly, when exposed to
air at room temperature, Al self-passivates and forms a thin stable
aluminum oxide (Al2O3) layer, which prevents the direct contact of
Al and carbon [23]. From XRD measurements (Fig. 3), the grain size
of Al in the HPed composites were found to be approximately
93 nm, just under half the size of the grain of the pure AlMg5 bulk
material, as indicated in Table 1. The lattice strain values showed a
similar trend. It is understood that small grain and high lattice
strain values are the result of significant grain deformation induced
by high-energy milling.
The Vickers hardness of the HPed composites is more than twice
that of the pure AlMg5 bulk material. Their indentation modulus
was also higher than that of the pure AlMg5 bulk material, 73
instead of 53 GPa, respectively, as indicated in Table 1. The exper-
imental modulus of pure AlMg5 is lower than its theoretical
modulus (around 70 GPa). It is believed that the indentation
modulus means the modulus of the indentation, not the modulus of
the bulk AlMg5 materials. And those differences was also con-
taining with different experimental conditions and errors. How-
ever, the composite was enhanced over 30% of the modulus and
those enhancements could mainly be due to pinning effects (grain
growth restrictions) associated with the addition of the GO
reinforcements.
Fig. 4 shows SEM and TEM micrographs prepared perpendicu-
larly to the pressure direction of the HPed composites. Grain
boundaries were clearly observed after the chemical etching pro-
cess (5% NaOH) (Fig. 4 aec). It is worth to note that most of the
visible pores and crevasses were generated during chemical
etching, without which, no grain boundaries could be observed.
Nevertheless, TEM observation did not reveal any significant pores
or cracks in the composites. The composite grain sizes determined
by TEM were slightly different between about 20 and 200 nm that
those determined by XRD analysis (Fig. 4def and Table 1). However
the XRD and TEM average values are showing the same tendency.
As can be seen in Fig. 4g, ten layers of stacked graphene oxide,
closely adhered to a matrix Al grain, were clearly observed in the
HPed composite.
810 H. Kwon et al. / Journal of Alloys and Compounds 698 (2017) 807e813
Fig. 4. (a) SEM micrographs of a representative AlMg5-1vol% GO composite, (b and c) SEM images of its microstructure, (def) TEM micrographs of the composite and (g) high-
resolution TEM of graphene oxide with an FFT (inset bottom right).
In general, graphene oxide typically retains the layered struc-
ture of its parent graphite. However, the layers seen in Fig. 4g are
buckled and their interlayer spacing (~0.7 nm) is approximately
twice that of graphite [24]. The thickness of the GO (FFT is also
indicated) layers was observed to be approximately 1.1 nm. Both
values are well in agreement with the values generally reported in
the literature [25].
Furthermore, the raw GO dry powder, the AlMg5-1vol% GO
powder blend and of the HPed bulk AlMg5-1vol% GO composite
were characterized by Raman spectroscopy (Fig. 5). The typical
Raman spectrum of a single-layer graphene has a defect-induced
peak (D-band, 1350 cm1), a sp2-induced peak (G-band,
1585 cm1), and a second order D peak (2D-band, 2685 cm1).
Indeed, the 2D peak is always present in graphene [26]. In general,
the quality of a graphene sample can be evaluated through the
relative intensities of the D- and the G-bands. The graphene oxide
used in this study showed a 2D peak smaller than the G-one,
meaning that the raw GO contains some amount of few-layer thin
sheets of graphene oxide (Fig. 5). However, no 2D-band was
observed in the powder blend and in the bulk composite. The ball
milled powder blend showed a higher D-band peak intensity
Fig. 5. Raman spectra of the GO powder, the AlMg5-1vol% GO powder blend, and the
AlMg5-1vol% GO composite.
relative to the G-peak compared to the raw GO. This may result
from a damage of the graphene structure during high-energy me-
chanical ball milling. However, the presence of the G-band means
that the graphitic structure of GO was still present in the Al alloy
matrix after milling. The D and G-bands could not be observed
anymore in the bulk composite. It is then worth to note that small
quantities of GO are investigated, only 1 vol% in the AlMg5 matrix.
Moreover, during milling, the GO particles are at least partially
damaged and also embedded into the soft aluminum grains. The
primary laser beam can in last case not reach the GO structure
anymore. These effects may be enhanced by the hot compaction
densification process.
Finally, the mechanical performances of the elaborated com-
posites were assessed through tensile and bending tests. For each
composite plate, three tensile samples were prepared and all the
tested samples showed similar stress-strain curves. This repro-
ducibility indicates that the GO was homogeneously dispersed
throughout the AlMg5 matrix. An example of the tensile response
of the AlMg5-1vol% GO composites is shown in Fig. 6. The average
tensile strength and elongation exhibited were approximately
560 MPa and 10%, respectively. This average strength value is over
two times that of pure bulk AlMg5 densified under the same hot
pressing conditions (around 230 MPa, Table 2). Yield strength
increased from 130 MPa for bulk AlMg5 to approximately 200 MPa
in the composite. However, the elongation at rupture of the com-
posites was approximately 40% lower than that of pure bulk AlMg5.
The bending properties of the AlMg5-1vol% GO composite were
measured using a four-point bending test. Pure bulk AlMg5 was
also tested for comparison. The results are summarized in Table 2.
The flexural strength obtained for the composites was almost
four times higher than that of pure bulk AlMg5 and reached a
strength around 800 MPa. However, the composite's deflection
values were much lower than those of pure bulk AlMg5 even
though in the latter case the tests had to be stopped because the
deformation exceeded the testable range (Fig. 7). One composite
sample out of the three tested showed a yielding effect with two
tangents (ly and ld) as shown in Fig. 6b [27], while the two other
samples did not (Fig. 7c).
In general, strengthening mechanisms of metals includes work
hardening, grain boundary strengthening, solid solution
 H. Kwon et al. / Journal of Alloys and Compounds 698 (2017) 807e813 811

concept of critical fiber length. The improved tensile strength of the

composites (GO fibers were regarded as discontinuous and unidi-
rectional fibers) is calculated by the Kelly-Tyson equation as
follows:
   
lc
sc ¼ sf Vf 1  þ s0 m 1  Vf (2)
2l

Fig. 6. Tensile strength of three samples of a representative AlMg5-1vol% GO
composite.
strengthening, precipitation hardening, and dispersion strength-
ening. For composites containing continuous, unidirectional fibers,
the tensile strength can be predicted according to the simple rule of
mixtures [28],
 
sc ¼ sf vf þ 1  vf sm
where sc is the tensile strength of the composite, sf is the tensile
strength of the fibers, vf is the volume fraction of the fibers, and sm
is the matrix stress at the failure strain. We define the failure strain
as the strain at the maximum stress. In this approach, the basic
assumptions are that fibers and matrix are perfectly bonded and
that the strain in the fibers is equal to that in the matrix. However,
in the case of discontinuous, unidirectional fibers, the strain in the
fibers and that in the matrix are not equal since the fibers are
separated by matrix materials at the fiber ends. Since the modulus
of matrix is lower than that of the fibers, the longitudinal strain is
higher than that in the adjacent fibers. One approach to deal with
this problem was proposed by Kelly and Tyson [29] using the
where Vf, sf, and sm represent the volume fraction of fibers, the
strength of fibers and the strength of the matrix, respectively. We
assumedsf to be 25 GPa [30]. In addition, Vf is 1 vol% and s0 m is
230 MPa lc represents the length of GO fiber when the composite
material is broken. It may be said thatlc is equal tol. The theoretical
value of sc is calculated to be 358 MPa, which is lower than the
experimental value. This difference could be because of the pres-
ence of other strengthening factors.
Furthermore, the enhanced yield strength of the composite
induced by grain refinement is estimated using Hall-Petch formula,
as follows [18]:
 
sGR ¼ K D0:5
C  D0:5
m (3)
where K is a constant (0.04 MPa for Al [18,31]), Dc and Dm are the
average grain size of the HPed composite and pure AlMg5,
respectively. sGR is calculated to be 38 MPa, which is much smaller
(1) than the improved yield strength of 200 and 610 MPa, as observed
from the tensile and bending tests.
However, theoretically calculated enhancement values are
much different from the experimentally achieved values. This im-
plies that another strengthening parameter accounts for the
strength increment of the HPed composite, with considerable and
reasonable errors between the experimental and theoretical con-
ditions. Further investigation of specific strengthening mechanism
should be investigated based on shear-lag model, Orowan looping,
thermal mismatch, clack bridging, and so on, which will be our next
project.
Fig. 8 shows SEM micrographs of the fracture surface of the
composite samples that demonstrated yielding and non-yielding
behaviors. More small dimples were observed at the surface of

Table 2
Measured mechanical properties of the hot-pressed pure AlMg5 and the graphene oxide reinforced AlMg5 matrix composites.

Samples Tensile test Bending test

Tensile strength 0.2% Yield strength Elongation Flexural strength 0.2% Yield strength Deflection
(MPa)±2.1 (MPa)±3.8 (%)±0.2 (MPa)±8.6 (MPa)±3.8 (mm)±0.08

AlMg5 Alloy Bulk material 260 130 25 210 150 0.99 (Stop)
AlMg5-1vol%GO composite 556 200 10 813 610 0.66

Fig. 7. Flexural strength and deflection of (a) bulk AlMg5, (b) AlMg5-1 vol% GO composite with yielding, and (c) AlMg5-1 vol% GO composite without yielding.
812 H. Kwon et al. / Journal of Alloys and Compounds 698 (2017) 807e813

Fig. 8. SEM micrographs of the fractured surface of (aec) the AlMg5-1vol% GO composite sample that exhibited yielding during the bending test and (c) the AlMg5-1vol% GO
composite sample that did not.

the non-yielding samples than at the surface of the yielding one, as
can be seen in Fig. 8c and f. In general, soft metallic materials
exhibit more significant dimple formations at fracture surfaces, as a
result of their high ductility compared to hard materials such as
ceramics. However, the different dimple ratios of these two com-
posite samples mean that the two samples had a different ductility.
Indeed, the ductility of the non-yielding samples was superior to
that of the yielding one (Fig. 7b and c). For all bending specimen,
some flat regions were found on their fracture surface as shown in
Fig. 8b and e (white circles). Such flat regions are generally
observed for brittle high strength materials.
The composition (GO dispersion) of the HPed AlMg5-1 vol% GO
composite was analyzed by EDS mapping (Fig. 9). Al, Mg, C, and O
were observed, Al and Mg being the main elements. It is very
difficult to observe individual nanosized carbon-based particles by
SEM-EDS because of spatial resolution limitations. However, with
EDS, it was possible to observe the carbon distribution despite the
nanosized nature of the carbon in the Al alloy matrix. The carbon
appeared to be uniformly dispersed throughout the composite, as
seen in Fig. 9e.
Considering that most of the carbon is coming from the starting
graphene oxide, from these characterizations, it seems that the
mechanical ball milling investigated here is an efficient process for
dispersing GO particles in Al alloy powders. The homogeneity of the
GO particles into the Al-matrix seems also to be confirmed by the
SEM and TEM observations as well as indirectly from the
outstanding mechanical performances of the composites. Gener-
ally, in metal matrix composites reinforced with nanoparticles the
strengthening is obtained by grain refinement, Orowan mecha-
nism, dislocation densities induced by thermal mismatch and load

Fig. 9. SEM micrographs and EDS analyses of the fracture surfaces of the AlMg5-1vol% GO composite. (a) SEM micrographs of the composite, and EDS maps of (b) aluminum, (c)
magnesium, (d) oxygen, and (e) carbon.
 H. Kwon et al. / Journal of Alloys and Compounds 698 (2017) 807e813
transfer [32]. In our case, no specific load transfer mechanism could
be observed on fracture surfaces and TEM analyses did not reveal
any particular differences in dislocation densities. However, it has
been demonstrated that the addition of GO enhanced the grain
refinement during milling as shown by the decrease of grain size of
the aluminum matrix. This is believed to be the main reinforcement
mechanism occurring in these composites. The dispersion of the
graphene oxide homogeneously in the matrix should also leads to
some Orowan strengthening.
4. Conclusions
Fully densified 1 vol% GO reinforced AlMg5 alloy matrix com-
posite materials were successfully fabricated by high-energy me-
chanical ball milling and hot pressing. Even if GO could not be
observed directly in the composite material, Raman spectroscopy
and EDS analyses showed that GO should be present and relatively
well dispersed in the Al-matrix. The mechanical performances of
the Al-alloy are clearly enhanced by the addition of only 1 vol% of
graphene oxide. The Vickers hardness of the composites is double
the hardness of the pure bulk AlMg5 alloy, and the ultimate tensile
strength of the nanocomposite reaches 560 MPa also over two
times higher than the strength of the alloy (230 MPa). The elon-
gation at rupture however decreases by 40% indicating a poorer
ductility of the composites materials. Moreover, the bending
strength of the composite is increased almost fourfold over this of
the pure bulk AlMg5 alloy. The mechanical performances obtained
here are over the reported strengths for the Al 5xxx series. How-
ever, even if it remains lower than the high strength aluminum
alloys, for instance a commercial 7001-T651 has typically a strength
of 620 MPa, the processing route investigated here is simple, up-
scalable and is not requiring costly precipitation or severe plastic
deformation hardening processes. Additional studies are ongoing
to better understand the strengthening mechanisms of these
composites and then further improve their performances.
Acknowledgements
This work was supported by a Research Grant of Pukyong Na-
tional University (2016 year) and this work was partly supported by
KACST, as well as by Estonian Ministry of Education and Science
projects TK117 and IUT2-24.
View publication stats
813
References
[1] S. Iijima, Nature 354 (1991) 56e58.
[2] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos,
I.V. Grigorieva, A.A. Firsov, Science 306 (2004) 666e669.
[3] H. Kwon, D. Park, J.F. Silvain, A. Kawasaki, Compos. Sci. Technol. 70 (2010)
546e550.
[4] H. Kwon, M. Estili, K. Takagi, T. Miyazaki, A. Kawasaki, Carbon 47 (2009)
570e577.
[5] A.M.K. Esawi, M.A. El Borady, Compos. Sci. Technol. 68 (2008) 486e492.
[6] J. Wang, Z. Li, G. Fan, H. Pan, Z. Chen, D. Zhang, Scr. Mater. 66 (2012) 594e597.
[7] S.F. Bartolucci, J. Paras, M.A. Rafiee, J. Rafiee, S. Lee, D. Kapoor, N. Koratkar,
Mater. Sci. Eng. A 528 (2011) 7933e7937.
[8] T.S. Sreeprasad, S.M. Maliyekkal, K.P. Lisha, T. Pradeep, J. Hazard. Mater. 186
(2011) 921e931.
[9] B.C. Brodie, Phil. Trans. R. Soc. Lond. A 149 (1859) 249e259.
[10] W.S. Hummers, J. Am. Chem. Soc. 80 (1958) 1339.
[11] http://en.wikipedia.org/wiki/Graphite_oxide.
[12] Y. Zhu, S. Murali, W. Cai, X. Li, J.W. Suk, J.R. Potts, R.S. Ruoff, Adv. Mater. XX
(2010) 1e19.
[13] Z. Li, Q. Guo, Z. Li, G. Fan, D. Xiong, Y. Su, J. Zhang, D. Zhang, Nano Lett. 15
(2015) 8077e8083.
[14] X. Gao, H. Yue, E. Guo, H. Zhang, X. Lin, L. Yao, B. Wang, Mater. Des. 94 (2016)
54e60.
[15] M. Rashad, F. Pan, D. Lin, M. Asif, Mater. Des. 89 (2016) 1242e1250.
[16] H. Zhang, C. Xu, W. Xiao, K. Ameyama, C. Ma, Mater. Sci. Eng. A 658 (2016)
8e15.
[17] I. Kruusenberg, J. Mondal, L. Matiesen, V. Sammelselg, K. Tammeveski, Elec-
trochem. Commun. 33 (2013) 18e33.
[18] EN-ISO 14577, Metallic Materials -Instrumented Indentation Test for Hard-
ness and Materials Parameters - Part 1: Test Method, 2003.
[19] EN-ISO 6892e1, Metallic Materials e Tensile Testing e Part 1: Method of Test
at Room Temperature, 2010.
[20] V. Uvarov, I. Popov, Mater. Character 58 (2007) 883e891.
[21] M. Ramezani, T. Neitzert, J. Achiev. Mater. Manuf. Eng. 55 (2012) 790e798.
[22] https://en.wikipedia.org/wiki/X-ray_fluorescence.
[23] H. Kwon, S. Cho, M. Leparoux, A. Kawasaki, Nanotechnology 23 (2012)
225704.
[24] M.J. McAllister, J.L. Li, D.H. Adamson, H.C. Schniepp, A.A. Abdala, J. Liu,
M. Herrera-Alonso, D.L. Milius, R. Car, R.K. Prudhomme, I.A. Aksay, Chem.
Mater. 19 (2007) 4396e4404.
[25] D. Pandey, R. Reifenberger, R. Piner, Surf. Sci. 602 (2008) 1607e1613.
[26] M.W. Iqbal, A.K. Singh, M.Z. Iqbal, J. Eom, J. Phys. Condens. Matter 24 (2012)
335301.
[27] D. Roylance, Stress-strain Curves, Massachusetts Institute of Technology
Study, Cambridge (, 2001.
[28] https://en.wikipedia.org/wiki/Rule_of_mixtures.
[29] A. Kelly, W.R. Tyson, J. Mech. Phys. Solids 13 (1965) 329e350.
[30] C. Cao, M. Daly, C.V. Singh, Y. San, Carbon 81 (2015) 497e504.
[31] D.H. Nam, S.I. Cha, B.K. Lim, H.M. Park, D.S. Han, S.H. Hong, Carbon 50 (2012)
2417e2423.
[32] R. George, K.T. Kashyap, R. Rahul, S. Yamadagni, Scr. Mater. 53 (2005)
1159e1163.