FlatChem 16 (2019) 100113

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FlatChem
journal homepage: www.elsevier.com/locate/flatc

Effect of graphene dispersion and interfacial bonding on the mechanical T

properties of metal matrix composites: An overview☆
Hanieh Ghodratia, Reza Ghomashchia,b,
⁎

a
School of Mechanical Engineering, The University of Adelaide, Adelaide, South Australia 5005, Australia
b
ARC Research Hub for Graphene Enabled Industry Transformation, University of Adelaide, Adelaide, SA 5005, Australia

ARTICLE INFO ABSTRACT

Keywords: The mechanical properties of metal matrix composites (MMCs) reinforced with graphene are very much de-
Metal matrix composites pendant on the uniform distribution of graphene in the matrix. The nature of bonding between the graphene
Graphene reinforcement and metallic matrices is also critical and influences the performance of the final composite. In
Dispersion spite of an abundance of information on graphene reinforced metal matrices, less attention has been made on the
Interfacial bonding
graphene dispersion and its interface bonding with the matrix. This is surprising as almost all reports cate-
Mechanical properties
gorically emphasize on their importance; however, specific attention to these issues is very scarce. This is the
main theme of this report to highlight the fundamentals of atomic structure of graphene as a contributing factor
on dispersion along with the bonding mechanism involved at the interface between graphene and the metallic
matrix. In the following sections, fabrication of metal-based composites reinforced with graphene through
powder metallurgy (PM) has been studied. In this respect, the challenges of dispersion and interfacial bonding
have been addressed in addition to their effects on the mechanical properties of composites. In this context,
recently developed novel methods including coating graphene with nano-metallic particles, vacuum filtration,
matrix-alloying, and defect engineering via plasma treatment along with their influence on mechanical prop-
erties have been discussed.

1. Introduction
In recent years, the incorporation of newly developed carbonaceous
nanomaterials such as carbon nanotubes (CNTs) and nano-graphite or
graphene (Gr) into metal matrices has introduced an important class of
advanced materials with superior mechanical and physical character-
istics [1]. These carbonaceous nano-sized materials with extraordinary
high elastic modulus and mechanical strength in addition to excellent
electrical and thermal conductivities are used for structural engineering
and functional device applications [1]. The unique mechanical prop-
erties of graphene and CNTs along with their large aspect ratio (i.e.
length to diameter, or length to thickness ratio), make them the most
effective reinforcing fillers in fabricating advanced composite materials
[1].
It was long believed that 2D crystals such as graphene to be ther-
modynamically unstable and could not exist [2]. The reason was related
to thermal fluctuations leading to displacement of atoms in low di-
mensional crystals at finite temperature [2–4]. These fluctuations be-
come as large as the force binding atoms together, causing the structure
to decompose or fall apart (the same type of force that cause melting ice
and losing its crystal structure above 0 °C) [2–4]. However, the synth-
esis of thermodynamically stable graphene by Geim and co-workers at
Manchester University in 2004, introduced a new dimension of research
in physics, chemistry and materials science [5,6].
Graphene (Gr) is a two-dimensional (2D) building block of graphite
composed of a single atomic layer of sp2 hybridized carbon atoms
(Fig. 1) [7]. The -stacking (an attractive, noncovalent interaction be-
tween aromatic rings) of graphene sheets holds the lamellar graphite
structure strongly in place [7]. Graphene with a honeycomb/hexagonal
lattice structure of the sp2-bonded structure has unique properties of
large surface area (2630 m2/g) [8], excellent mechanical strength
(Young’s modulus of 1 TPa) [9], high level of thermal conductivity
(above 3000 Wm−1K−1) [10] and electrical conductivity (2.5 × 105
cm2 V−1 s−1) [11]. Owing to such key features, graphene has become a
versatile carbon material promising for a wide range of applications
including high-performance nanocomposites [12,13], transparent con-
ducting films [5,14], sensors [15], nanoelectronics [16], and energy
storage devices [17].

☆
Conflicts of interest: The authors declare no conflicts of interest.
⁎
Corresponding author at: School of Mechanical Engineering, The University of Adelaide, Adelaide, South Australia 5005, Australia.
E-mail address: reza.ghomashchi@adelaide.edu.au (R. Ghomashchi).

https://doi.org/10.1016/j.flatc.2019.100113
Received 6 February 2019; Received in revised form 2 May 2019; Accepted 14 May 2019
Available online 20 May 2019
2452-2627/ © 2019 Elsevier B.V. All rights reserved.
H. Ghodrati and R. Ghomashchi
Fig. 1. Graphene sheet (a) wrapped into 0D bulky-balls, (b) rolled into 1D nanotubes, or (c) stacked into 3D graphite [2].
Fig. 2. Single walled carbon nanotubes (SWCNTs), double and multi walled CNTs [18].
In addition to its planar structure (Fig. 1), graphene can also be
‘wrapped’ into zero-dimensional bulky-balls (Fig. 1a), or rolled into a
single wall tube of carbon with a diameter of 1–2 nm (Fig. 1a) [2]. The
seamless cylindrical forms of graphene sheets are known as carbon
nanotubes (single and multi -walled carbon nanotubes Fig. 2) [18]. The
2D structure of graphene with large aspect ratio provides more area to
interact (from both sides of faces) with the matrix component com-
paring to CNTs [19,20]. Furthermore, the flat morphology of graphene
enables mechanical interlocking with matrix [21,22]. In addition to its
geometry, the availability and cost-effectiveness of graphene with high
quality are other important factors to be taken into account for re-
inforced structural composites [18,19]. Graphene can also be stacked
into three-dimensional graphite containing more than ten graphene
layers (Fig. 1c) [2]. Graphene can also become as nanoflakes and na-
nosheets in terms of few layers of sheets held together in thickness
direction. This is referred as graphene platelets (GPLs)/graphene na-
noplatelets (GNPs) or graphene nanosheets (GNS) with average thick-
ness of 5–100 nm [18].
In spite of many reports in open literature on the importance of
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FlatChem 16 (2019) 100113
incorporating graphene and CNTs in metal matrices and fabrication of
nanocomposites, there are no such reports to specifically address the
importance relevant to distribution of graphene and CNTs in nano-
composites. In this article the significance of graphene regarding its
electronic structure, the nature of bonding between graphene and metal
matrices as well as the bonding mechanism will be discussed in details.
In the following, the effect of dispersion and interfacial bonding on
mechanical properties of the final composite will be highlighted. We
will then look at the solid state processing i.e. powder metallurgy (PM),
and its challenges to disperse graphene into the matrix. In this regard,
the recent novel approaches will be discussed to overcome difficulties
associated with distribution of graphene into the metallic matrices as
well as interfacial bonding.
2. Synthesis of graphene
There are different fabrication methods to produce graphene in-
cluding exfoliation (physical/mechanical or chemical), epitaxial growth
via chemical vapour deposition (CVD), and the unzipping of CNTs [23].
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Fig. 3. Schematic representation of the mechanism for CVD Graphene growth on Ni [33].

Fig. 4. Producing Graphene from unzipping MWCT [32].

a) b) c)
2px 2py 2pz 2pz
2p
sp3 sp2
Energy

2s
Hybridisation

1s 1s 1s

Fig. 5. Energy level diagram for carbon atom. The four valance electrons in the doubly occupied spherical 2 s orbital and the half occupied dumbbell-shaped 2p-
orbitals take part in the formation of the chemical bond. a) Ground-state diagram, b) sp3 hybrid orbitals in diamond, c) sp2 hybrid orbitals in graphite and graphene
[35].

3
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Side view Top view

Fig. 6. The orientation of three sp2 hybrid orbitals in carbon with three coplanar hybrid orbitals at angle of 1200 to each other. The one unchanged p orbital is
perpendicular to the plane of the hybrid orbitals [36].

Fig. 7. Hexagonal lattice of graphene (left) where a1 and a2 are the lattice vectors and i, i = 1, 2, 3 are the nearest-neighbor vectors. Corresponding Brillouin zone
(right) where K and K ' are the Dirac points [37].

a)

Fig. 8. a) and bonds in graphene [39], b) Electronic dispersion and bands in the honeycomb lattice obtained from tight-binding approach. These bands have
linear dispersion in the vicinity of the K points of the Brillouin zone of graphene. [35].

Since fully detailed discussions on the synthesis of graphene can be
found in a number of reviews [23–27], we briefly referred to such
methods and stay focused on metal-based composites reinforced with
graphene.
an intercalation1 between graphite sheets and afterwards ethanol ap-
plied for exfoliation to produce graphene sheets [29] or the mechanical
method used by the Noble laureates Andre Geim and Konstantin No-
voselov of University of Manchester (2004), using a Scotch tape to pull
off graphite sheet, graphene.

2.1. Exfoliation

Exfoliation is a peeling process where breaking van der Waals bonds

between layers of graphite occurs either chemically or mechanically
[28]. This means graphene can be produced through breaking stacked 1
Intercalation may be defined as the inclusion or insertion of a molecule
layers of several graphite sheets [26]. For instance, potassium used as between the layers of a lamellar material such as graphite

4
H. Ghodrati and R. Ghomashchi
Fig. 9. The metal-graphene contact and corresponding charge transfer (n-doped
graphene) through physisorption. “Before” and “after” charge transfers are two
sequential steps taking place in real interface interactions. Here, they have been
shown as separated steps to have a better physical illustration [48].
2.2. Chemical vapour deposition (CVD)
Chemical vapour deposition (CVD) is a heterogeneous reaction
where graphene is deposited on a substrate (usually transition metals
e.g. Ni or Cu) through exposure to volatile precursors (precursor gases/
carrier gases) at a high temperature [30]. As illustrated in Fig. 3, the
substrate is exposed to the hydrocarbon vapour in the presence of argon
as the carrier gas followed by pyrolysis at 700–850 °C [30]. The gas
diffuses in the substrate and upon cooling of the substrate, the carbon
precipitates out on the surface to form graphene sheets on the surface of
the substrate [31].
Fig. 10. Optical micrographs displaying the effect of the addition of GNP on the grain size of pure Cu (a) reduced the grain size (b) with 8 vol-% GNP/Cu [66].
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FlatChem 16 (2019) 100113
2.3. Unzipping CNTs
This technique has been developed recently to produce graphene
from multiwall carbon nanotubes (MWCNT). The MWCNT as precursor
can be opened longitudinally by intercalation of Li, Na and ammonia.
This follows by acid exfoliation and annealing at high temperature
(Fig. 4) [32].
3. Metal-graphene interface
The integrity of composites is very much dependent on the re-
inforcement-matrix interface characteristics as the structure, crystal-
lographic, physical and chemical nature of the interface affect the bond
strength and thus the final properties of the composite. Once the matrix
and reinforcing agent are selected, the interface needs to be engineered
to achieve the desired properties. The interface which is defined as “a
surface across which a discontinuity occurs in one or more materials para-
meters or properties, e.g. atomic lattice, density, mechanical characteristics
(E, KIC, etc.)” has two distinct features;
1. Occupies a large area in composites
2. The reinforcement/matrix interface forms a system that is not in
thermodynamic equilibrium [34]. This may act as the driving force
for diffusion to induce dissolution and/or chemical reaction if op-
timum kinetics condition (i.e. a high enough temperature or long
enough time) is given [34]. A state of thermodynamic equilibrium at
the interface is preferential.
It is well established that, upon a strong interfacial bonding between
components a more efficient load transfer occurs from the matrix to the
reinforcement. The nature and characteristics of the interface between
the reinforcement and matrix significantly affect the mechanical
properties of composites [34]. The nature of interface may be coherent
(crystal lattice at the interface is oriented in similar directions as the
composite constituents – highly strained structure), semi-coherent
(dislocations at interface) and in-coherent (disorder). Regarding the
nature of bonding at the interface, basically, there are two types of
chemical and physical (mechanical) bonding. For physical bonding, the
bond energy is low and independent of temperature. It is weak van der
Waals and hydrogen bonds, while the chemical bonding is strong (bond
energy is one order of magnitude greater than physical bond). In con-
trast to physical bonding, chemical bonding is irreversible and tem-
perature dependant. It requires the transport of atoms across the
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Table 1
Effect of dispersion and processing techniques (Powder Metallurgy) on mechanical properties of graphene reinforced metal matrices (Al, Cu, Mg).
Composition Dispersion and Fabrication Process Mechanical Properties References

Al–0.1 vol-% GNP
Al2024–xvol.-% GNP (x = 0,
0.25, 0.5, 1.0)
Al alloy xvol.-% GNP (x = 0,
0.15, 0.5)
Al6061 1.0 vol-% GNP
Al2024–xvol.-% GNP (x = 0,
0.3, 0.5, 0.7)
Al–xvol.-% GNP (x = 0, 0.5, 1.0,
1.5, 2.0)
Al–xvol.-% GNP (x = 0, 0.25,
0.5, 1.0)
Al alloy xvol.-% GNP (x = 0, 0.3,
0.5, 0.7)
Al xvol.-% GNP (x = 0, 0.5, 1.0,
3.0, 5.0)
Cu xvol.-% GNP (x = 3.0, 5.0,
8.0, 12.0)
Cu xvol.-% GNP (x = 0.5, 1.0)
Cu xvol.-% GNP (x = 1.0, 2.0)
Cu xvol.-% GNP (x = 0.5, 1.0,
2.0)
Cu 2 vol-% GNP
Mg–x vol.-% GNP (1, 2, 5)
Mg–1%Al–1%Sn 18.0 vol-% GNP
Mg–0.64Al–x vol.-% GNP
(x = 0.07, 0.15, 0.30)
Mg–1Cu–xGNPs (x = 0.18, 0.36,
0.54)
Mg alloy (AZ91) xvol.-% GNP
(x = 0.1, 0.3, 0.5, 0.8, 1.2)
Blending the Al powder and GNP, ball milling, hot isostatic Reduction in hardness and tensile strength. 63
pressing at 375 °C and then hot extrusion at 550 °C.
Ball milling Al powder and GNP for 1, 3 and 5 h – compacted at Improvement in hardness ∼138% with 1.0 vol-% GNP for 67
950 MPa – sintered in Ar atmosphere for 0.5, 1, 2, 3, 4 and 5 h at 5 h milling and 2 h sintering.
500 °C.
Ball milling Al powder and GNFs dispersed in ethyl alcohol at Improvement in YS ∼49% with 0.5 vol-% GNP. 61
75 rpm for 12 h, drying the mixture slurry – Hot isostatic pressing
at 480 °C and 110 MPa for 2 h- Hot extrusion at 450 °C for 1 h.
Mixing the Al powder and GNP by Ball milling at various times 10, Improvement in flexural strength by 47% and 34% for the 78
30, 60, and 90 min – pre-compaction at 50 MPa at room 60-min and 90-min times.
temperature – hot pressed at 100 MPa for 10 min at 630 °C.
Mixing graphene in the Al2024 powder by planetary ball milling Improvement in tensile strength by 50% with 0.7 vol-% GNP 64
at 100 rpm for 3 h following by the high-energy ball-milling in an and 4% elongation.
attritor at 500 rpm for 9 h – hot rolling at 450 °C.
The Al powder and GNP were mechanically mixed in blender at a Improvement in yield strength by 8.8% and ultimate tensile 86
speed of 17 rpm for 24 h – blended powder was cryomilled at a strength by 17.7% with 0.5 vol-% GNP.
rate of 180 rpm for 2 h, and finally hot vacuum degassed – hot Reduction in elongation by 8% with 0.5 vol-% GNP The
extruded at 300 °C – annealed at 300 °C for 2 h. strength of Al/Gr with 1.0 wt% GNFs did not decrease
relative to 0.5 wt% GNFs.
GNPs dispersion by ultrasonication in ethanol added to Al slurry Before extrusion, Improvement in UTS ∼13.5% and failure 87
in ethanol, stirring by mechanical agitator at 2000 rpm for 1 h, strain ∼50%, with 0.25 vol-% GNP.
filtering and vacuum dried – pressing and sintering at 600 °C – hot After extrusion, reduction in UTS ∼10.8%, and
extrusion at 470 °C. improvement in failure strain ∼46%
Al powder and GNP ball milled at 200 rpm for 1 h, 100 rpm for 3 h Improvement in YS ∼71.8% with 0.7 vol-% GNP. 65
and 500 rpm for 6 h – milled powder was containerised in Cu tube
–compacted – hot rolled at 500 °C.
GNPs dispersed uniformly in Al matrix using ultrasonication – Improvement in hardness by 21.4%, YS by 84.5%,and tensile 56
dried powder sintered in spark plasma sintering furnace (SPS) at strength by 54.8% with 1 vol-% GNP
maximum pressure and temperature of 50 MPa and 550 °C.
Ball milling and mixing GNPs with Cu powder at 1200 rpm for Improvement in Young’s modulus by 37% and yield strength 66
3 h–hot pressing and sintering at 800 °C for 15 min and 40 MPa. by 114% with 8.0 vol-% GNPs.
Ultrasonication of Cu and GNP in ethanol for 1 h – dried and ball Improvement in UTS ∼10.7% by and YS ∼14.7% by 62
milled for 400 rpm for 4 h– high-ratio differential speed rolling with 1.0 vol-% GNPs.
(HRDSR).
Ball milling for 5 h – hot pressing of 550 MPa at 510 °C. Improvement in hardness by 50% with 2.0 vol-% GNPs. 68
Ball milling of Cu powder and GO at 400 rpm for 1, 3, 5, and 7 h – Improvement in UTS ∼28% by and YS ∼14.7% by 69
hot pressing at 850 °C for 1 h with 25 MPa. with 0.5 vol-% GNPs.
Ball milling Cu and RGO for 8 h and 16 h – pressing and sintering Improvement in hardness by 20%. 70
at 750 °C.
Ball milling at 350 rpm for 15 min – pre-pressed at 5 MPa – Improvement in hardness ∼ 37% reduction in compressive 79
sintered at 450 °C, 50 MPa. strength ∼8.6% with 2 vol-% GNP.
Ultrasonication for 1 h, mechanical agitation for 1 h- Compaction Improvement in UTS by ∼14% and yield strength by 76
under 580 MPa and sintering at 630 °C for 2 h – Hot extrusion at ∼29.2%.
350 °C.
Mixing of Mg–0.64Al powder with GNP in ethanol and Improvement in hardness ∼34% 77
mechanically agitating – the mixture is filtered and vacuum dried Young’s modulus ∼ 131%
overnight at 70 °C – the powder is compacted, sintered at 630 °C YS ∼50%, failure strain ∼ 74.2% with 0.3 vol-% GNP.
and hot extruded at 350 °C.
Mixing Mg and Cu (wt-1%) powders in ethanol by high speed Improvement in hardness by ∼42%, elastic modulus by 75
mechanical agitator (2000 rpm), mixing GNPs with the Mg-1Cu 89%, yield strength by 117%, ultimate tensile strength by
and mechanical agitation for 1.5 h, then filtered and dried – 58%, and failure strain by 96% with 0.54 vol-% GNP.
compaction (600 MPa) and sintering at 630 °C for 3 h.
Ultra sonication of GNS and AZ91 in ethanol for 1 h, filtered and Improvement in yield strength by 76.2% and elongation by 80
dried – presses, sintered, and hot extrusion. 24.3% with 0.5 vol-% GNPs.

interface and is diffusion controlled. The reaction zone thickness ( X ) is
time (t ) dependants as;
X 2 = Dt
where D , the diffusion coefficient is temperature dependent expressing
as;
Q
D = D0 exp
RT
D0 = pre-exponential factor (m2/s), Q = activation energy (J/mol),
R = gas constant (8.31 J/mol.K) and T = temperature (K).
In the next part, the fundamentals of electronic properties of the
graphene/metal interface will be discussed in addition to the me-
chanism of the interfacial reaction with the metal matrix. Graphene is
an allotrope of carbon, and to gain deeper insight into the metal-gra-
phene interfacial bonding, it is helpful to examine the electron con-
(1) figuration of carbon, and the atomic structure of graphene.
3.1. Atomic and electronic structure of carbon and graphene
Carbon has the atomic number 6 with ground-state electron con-
(2)
figuration (the lowest energy distribution/arrangement of electrons in
atomic orbitals) of (1 s)2(2 s)2(2p)4 [35]. The 2 electrons in 1 s orbital
are core electrons remaining more or less inert, but the valance elec-
trons in 2 s orbital and three 2p orbitals can hybridize through com-
bination of these atomic orbitals (hybridization) [35]. Fig. 5 shows the
energy level diagram (electrons occupy discrete/quantized values of

6
H. Ghodrati and R. Ghomashchi
Fig. 11. Raman spectra for as-milled Al-GNPs (1.0 wt%) for 1, 3 5 h of milling
time [67].
energy) for the C in ground state, sp3 hybrid orbitals, and sp2 hybrid
orbitals [35]. Bonding of C with other C atoms occurs through pro-
motion of one of the 2 s electrons into the empty 2pz orbital [35]. Thus,
the general interest of carbon arises from this electron configuration of
C forming different ways of bonding in the solid state through atomic
orbital hybridization [35]. In diamond, for instance, hybridisation of
one s orbital and three p orbitals gives four energetically equivalent sp3
hybrid orbitals. The four sp3 hybrid orbitals are arranged in the tetra-
hedral arrangement so that electrons undergo the minimum repulsion
[35]. The three-dimensional structure of diamond forms by the overlap
between sp3 hybrid orbitals of one carbon atoms with the sp3 hybrid
Fig. 12. SEM micrograph for ball-milled Al–1 wt-% GNP powders showing the morphology for (a) Al – 1 h, (b) Al – 5 h, (c) Al–1 wt-% GNP – 1 h, and (d) Al–1 wt-%
GNP – 5 h [67].
7
FlatChem 16 (2019) 100113
orbitals of other carbon atoms. The strong binding energy of the C–C
bonds (345 kJ/mol) in diamond results in high hardness [35].
In graphite and graphene, hybridisation of one s orbital and two p
orbitals gives three sp2 hybrid orbitals leaving one p orbital (by con-
vention 2pz) unhybridised [35,36]. The three sp2 hybrid orbitals lie in
the same plane separated by 1200 angel, and the unchanged/un-
hybridized p orbital is perpendicular to the plane of the hybrid orbitals
(Fig. 6) [35]. Thus, sp2 hybrid orbitals of each carbon in graphite and
graphene form three covalent in-plane -bonds with three carbon
neighbours and one covalent bond by out of plane (parallel) or-
ientation of unhybrized p orbital [35,36]. This form of C bonding in
graphite and graphene results in the planar hexagonal “honeycomb”
structure of graphite [35]. Comparing the strength of bonding between
graphite and diamond, the in-plane -bonds within the graphene layers
(615 kJ/mol) are stronger than C–C bonds in sp3 orbital hybrids in
diamond (345 kJ/mol) [35]. However, the bonds formed by the un-
hybradised p orbitals in graphite have a significantly lower energy
comparing to -bonds due to parallel orientation of p orbitals (less
overlap between the component p orbitals). This leads to graphite
layers to be easily sheared along the plane [35,36].
The hexagonal structure of graphene can be viewed as triangular
lattice containing a basis of two atoms per unit cell (Fig. 7) [37]. The
lattice vectors are given by
a a
a1 = (3, 3 ), a2 = (3, 3)
2 2 (3)
where a = 1.42 Å is the shortest distance between two carbon atoms i.e.
C–C distance [37]. The reciprocal lattice vectors b1 and b2 can be
written as (Fig. 7)
2 2
b1 = (1, 3 ), b2 = (1, 3)
3a 3a (4)
H. Ghodrati and R. Ghomashchi
Fig. 13. a) Composite powder (Al-1wt% GNP) and Fracture surface analysis (FE-SEM micrographs) of SPS consolidated composite powder (b) Al, (c) Al-GNP (0.5 wt
%), (d) Al-GNP (1 wt%), (e) Al-GNP (3 wt%), and (f) Al-GNP (5 wt%) [56].
The two points K and K ' at the corners of the graphene Brillouin
zone (the primitive cell in the reciprocal space) are called Dirac points
[37]. Their positions in the momentum space (reciprocal space; Fourier
transform of “real space” to reciprocal space) are given by [37]
2 2 2 2
K= , , K' = , (K or K ' point in the BZ) [35].
3a 3 3 a 3a 3 3a (5)
As can be seen from Fig. 8, each carbon atom in the graphene
honeycomb structure is connected to the three neighbour atoms
through strong covalent sp2 or bond [35]. The remaining electron in
2pz orbital ( orbital) which is perpendicular to the plane of graphene,
determine the low-energy electronic structure of graphene [35,36]. The
dispersion of the electrons in graphite building layer, now referred
graphene, was calculated by the tight-binding approximation in 1947
considering the unit cell of graphene contains two orbitals [38].
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FlatChem 16 (2019) 100113
These orbitals disperse to form two bands as bonding (the lower energy
valance band) and anti-bonding (the higher energy conduction band)
(Fig. 8) [35]. Thus, the three-dimensional energy band structure of
graphene is displayed in Fig. 8. It can be seen that the valance and
conduction bands do not separate but meet each other at Dirac points
Therefore, graphene has a unique electronic structure in which the
and bands meet in a single point at the Fermi energy (it is situated
at the energy level where the valance and conduction bands meet [35])
at the corner of Brillouin zone (Dirac point). The bands show a linear
dispersion at the K and K’ zone [40]. However, the electronic structure
of graphene can be significantly distorted upon the interaction of gra-
phene with metallic particles [40]. Based on the nature of bonding at
the interface, it can be either strongly chemical bond or weakly physical
bond. In the following section, the mechanism of such bindings at the
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Fig. 14. Optical micrographs of cross section of SPS sintered pellets for a) Al, b) Al – 0.5 wt% GNP, c) Al – 1 wt% GNP, d) Al – 3 wt% GNP and e) Al – 5 wt% GNP [56].

Fig. 15. Yield strength and Young’s modulus of GNP/Cu composites as a

function of GNP volume fraction [66]. Increasing from 8 vol% GNP to 12 vol% Fig. 16. Raman spectra of pristine GNPs, Cu–GNP powder, and sintered com-
GNP caused significant reduction in yield strength from 114% to 46% due to posites. The increase in defect (ID/IG) on milling of Cu–GNP powder as com-
agglomeration of GNP in the Cu matrix [66]. pared to pristine GNP, while sintering showed no significant change [66].

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H. Ghodrati and R. Ghomashchi
Fig. 17. Optical micrographs of a) pure Mg, b) Mg–1Cu–0.18GNPs, c) Mg–1Cu–0.36GNPs and d) Mg–1Cu–0.54GNP composites [75]. The grain size reduces with the
increase in the GNP contents [75].
interface discussed.
3.2. Mechanism of interfacial bonding
In recent years, there have been intensive studies on the sorption of
transition metals on graphene based materials [41]. These types of
graphene hybrids can have device applications in microelectronic de-
vices for catalysis or energy storage [41].
The graphene and metal can form a physisorption interface with
mechanism of charge transfer [42–44] or a chemisorption interface
through orbital hybridization [43–47]. In the work by Gong et al. [48],
ab initio method was undertaken to provide the fundamentals of elec-
tronic properties at such interfaces. In the physisorption (weak inter-
action) interface, the graphene’s -band structure with linear band
crossing at Dirac point (K and K’) is maintained, but the Fermi level
moves corresponding to the Dirac point [48]. For the weak physisorp-
tion interfaces, the primary effect is due to Pauli exclusion interaction
between graphene -electrons and the metal s-electrons [48]. The Pauli
exclusion will be induced by approaching the metal surface atoms to
graphene. So the metal’s s-electrons in the outermost occupied shell will
overlap with graphene’s -electrons [48].This repulsive interaction
pushes the electron density back into both metal’s and graphene’s
subsurface away from the interface [48]. The change in the relative
shift down of graphene’s energy-levels is negligible, and so the work
function (WF) decrease in graphene is negligible [48]. This is due to the
fact that graphene is a surface-like material without accumulation of a
large number of electrons, and also redistribution of π-electrons needs
hybridization with s-electrons which is not energetically favourable
[48]. On the contrary, redistribution of the electron density at the metal
surface occurs through rehybridization of the surface electronic orbitals
resulting in a larger WF decrease [48]. Therefore, there is a new “dis-
crepancy” between metal-graphene complex’s Fermi level and gra-
phene’s charge neutrality level (Dirac point) [48]. To reduce this
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FlatChem 16 (2019) 100113
discrepancy, a charge transfer (self-compensation mechanism) occurs at
the interface from metal to graphene or vice versa depending on the
relative shift of WFs [48]. When charge transfer happens, the gra-
phene’s energy-levels (Fermi levels) shifts up (n-doped graphene) or
shift down (p-doped graphene) with respect to conical points [48]
(Fig. 9).
For chemisorption interface between graphene and metal, orbital
hybridization has the major role in band gap opening of graphene along
with contributions from Pauli exclusion interactions [48]. Due to Pauli-
exclusion interaction at interfacial distance the energy-levels of gra-
phene shift down further relative to that of metals [48]. The -electron
states of graphene starts to overlap with d-electron states of metal
leading to the hybridization interaction [48]. Thus, a strong hy-
bridization of metal’s d-orbital and graphene’s π-orbital perturbs gra-
phene’s electronic structure in chemisorbed graphene, and as a result of
this chemical interaction at chemisorption interfaces the electronic
structure is much more complicated [48].
Thus, the strong hybridization of graphene and metal’s orbitals at
the interface will cause the strong covalent chemical bonding where the
mixing of those orbitals is absent for the weak physical bonding as
discussed earlier. The strong interfacial bonding at the interface is
highly desirable to fabricate metal matrix composites reinforced with
graphene. The strength of physical and chemical interfacial bonding is
discussed in the following section, along with the importance of
strength on the mechanical properties.
3.3. Strength of interfacial bonding
As mentioned above, the most widely used approach to study gra-
phene/metal interface strength is based on theoretical approach ap-
plying the first-principles density functional theory (DFT) calculations
[42,48–51]. In order to measure the strength of interaction between
graphene and metallic surfaces, the bonding energy per carbon atom,
H. Ghodrati and R. Ghomashchi
Fig. 18. SEM images for (a) pure Mg showing large grains with very clear grain boundaries; (b–d) Mg–1Cu–0.36 GNPs, showing presence of the second phase due to
limited solubility of Cu in Mg, which prevented grain growth [75].
the state of the Dirac cone or the doping level (defined by the position
of the Fermi level with respect to the Dirac point) can be used [48–51].
Considering DFT calculations for weakly physisorbed interfaces be-
tween graphene and metals such as Al, Ag, Cu, Cd, Ir, Pt, and Au, ad-
sorption energies are around 0.03–0.05 eV per carbon atom, with
equilibrium interfacial distances > 3.0 Å [42,48–51]. In contrast, for
chemisorption interfaces (strong interaction) between graphene and
metals formed including Ni, Co, Ru, Pd, and Ti, adsorption energies are
larger at around 0.09–0.4 eV per carbon atom, with smaller equilibrium
interfacial distances < 2.5 Å [42,48–51]. The values reported by
[42,48–51] are in agreement with previous calculations and experi-
mental data [46,52–55]. Comparing calculated values of energies,
chemical bonding at the interface is much stronger than physical
bonding as expected.
Considering the importance of interfacial strength on mechanical
properties, it is the key parameter in facilitating the stress transfer from
the metallic matrix to the reinforcement (load transfer) in metal-gra-
phene nano-composites [56,57]. The effect of interfacial bonding can
be explained by shear lag model that explains the load transfer in
metals reinforced with graphene [58,59]. The tensile stress experienced
11
FlatChem 16 (2019) 100113
by the composite creates an interfacial shear stress, and the stronger
interfacial bonding can facilitate better stress transfer from metal ma-
trix to the graphene upon approaching the interface [56,60]. This can
prevent graphene from being broken or pulled out [56,60]. The in-
creased yield strength calculated from shear lag model is expressed in
the following equation;
S
SL = m + fv m
2 (6)
where SL , fv , m , , and S are yield strength of composite, volume
fraction of GNP, yield strength of matrix, and aspect ratio of GNP, re-
spectively. However, reinforcing efficiency is proportional to interface
strength and the size of graphene nano-platelets play a role on the
strength of the composite. In addition to the strong interfacial bonding,
it is well established that uniform distribution of graphene in the me-
tallic matrix also plays a key role in improving the mechanical prop-
erties of composites. However, it is quite difficult to achieve uniform
dispersion of GNPs in a metal matrix with strong interfacial bonding
due to their high specific area and van der Waals interaction between
graphene nanosheets [1,22].
H. Ghodrati and R. Ghomashchi
Fig. 19. TEM images, SAD pattern and EDS spectrum for Mg–1Cu–0.36 GNPs composite displaying formation of Mg2Cu intermetallic phase [75].
Fig 20. Comparison between experimental values and theoretical calculations
of Young’s modulus from equation Halpin–Tsai equation for GNP/Cu compo-
sites as a function of GNP volume fraction (Eq. (1) and (2) are in ref. 73) [66].
4. Graphene dispersion
As mentioned before graphene dispersion plays an important role in
fabrication and integrity of advanced graphene reinforced nano-com-
posites. The dispersion however can only be expressed in the context of
the fabrication route.
To date, the conventional process of powder metallurgy (PM) ex-
hibited important role in fabrication graphene reinforcing metal matrix
composites. The initial stage of PM is grinding and blending graphene
reinforcing component with metal powders via milling processes either
in wet [61] or dry [62] conditions. It is then followed by consolidation
and sintering processes as combined or separated steps such as hot
extrusion [61,63], hot isostatic pressing [61,63], hot rolling [64,65],
12
FlatChem 16 (2019) 100113
spark plasma sintering [56] or performed conventionally in controlled
environment furnaces or in microwave ovens.
In various PM processes, the only step to produce uniform disper-
sion is the initial powders mixing stage, and so the next steps of com-
paction, sintering and other processes do not generate homogeneous
dispersion [1]. Thus, the initial powder mixing has great impact on the
final performance of the MMCs. The reason is that well-distributed
graphene leads to strengthening the composite through grain refine-
ment (pinning effect). The uniformly distributed GNPs on grain
boundaries and inside of grains lead to pinning the grains boundaries by
GNPs and restricting grain growth during sintering [19,56]. Thus,
uniform mechanical behaviour throughout the structure obtains by
homogeneous grain size dispersion in the composite structure [56]. The
following well-known Hall-Petch relationship presented in equation
(10) explains the strengthening achieved by grain refinement [61].
ky
y = 0 +
d (7)
where, d is the mean grain size, y is the yield strength (YS), and 0 and
k y are constants specific for a material. For example, the yield strength
of GNP/Cu with respect to pure Cu increased by 114%. This was
achieved by a 60% reduction in the grain size of Cu (Fig. 10) through
addition of 8 vol.% GNP [66].
Nevertheless, uniform incorporation of GNPs into metal matrix has
remained a difficult task. One reason is attributed to the agglomeration
or clustering of GNPs in the metal matrix due to their large surface area.
To reduce surface energy, clustering of GNPs occurs upon the process of
mixing in a metal matrix [1]. Another reason for such tendency of ag-
glomeration is the presence of van der Waals forces which is 2 eV/nm2
between graphene sheets [1,22]. The final obstacle of uniform dis-
tribution is because of partial remelting during sintering (liquid phase
sintering). This may result in altering the uniform distribution of GNPs
obtained during powder mixing due to; a) poor wetting of carbonaceous
materials with most metallic melts (large contact angles > 90°) [1]
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Table 2
Recent novel methods to improve dispersion and interfacial bonding between GNPs and metal matrix.
Composition Dispersion and Fabrication Process Mechanical Properties References

Cu–4.7 vol-% RGO
Cu–0.8 vol-% RGO-Ni
Cu–xvol.-% RGO-Ni (x = 0.94,1.88)
Cu–0.5 vol-% GNP-Ni
Cu–0.5 vol-% GNP-Cu
xvol%Mo2C-RGO/Cu (x = 1)
Al–xvol.-% RGO-Cu (x = 3,5)
6061Al–xvol.-% GNP-Ni(x = 0.5,0.7,1.0)
Hummers method to oxidize graphite to GO Improvement in tensile strength 107% and 90
Electroless Cu plating to decorate GO with CuPowders reduced at 400 °C Young’s modulus 21%.
for 5 h in a H2 atmosphere
Spark plasma sintering.
Hummers method to oxidize graphite to GO Improvement in UTS by 42% with 0.8 vol-% 89
Electroless Ni plating to decorate RGO with Ni RGO-Ni.
Mixing RGO-Ni powder with Cu under sonication for 1 h
Spark plasma sintering.
Hummers method to oxidize graphite to GO Improvement in yield strength by 94% and 91
In situ chemical reduction method to decorate RGO with Ni Young’s modulus by 61% with 1.88 vol-%
Mixing RGO-Ni with Cu powder under sonication for 3 h RGO-Ni.
Spark plasma sintering.
Electroless Cu plating to decorate GNP with Ni Improvement in yield strength by 64.5% 94
Electroless Ni plating to decorate GNP with Cu with 0.5 vol-% GNP-Ni
Mixing GNP-Ni and GNP-Cu powders with Cu powder with mechanical Improvement in yield strength by 49.1%
stirring for 2 h with 0.5 vol-% GNP-Cu.
Spark plasma sintering.
Thermal annealing to produce Mo2C-RGO Improvement of yield strength by 127% 93
Mixing Cu and Mo2C-RGO powders with low-energy ball milling
Spark plasma sintering.
Hummers method to oxidize graphite to GO Improvement in tensile strength by 77.5% 92
Molecular level mixing to decorate RGO-Cu and hardness by 29.1% with 3 vol-% GNP-
Clad rolling at 500 °C. Cu.
in situ chemical vapour deposition to decorate graphene with Ni Improvement in yield strength 75% and 60
nanoparticles ball milling for 90 min to mix GNP-Ni and 6061 Al powders tensile strength 30% with 0.7 vol-% GNP-Ni.
hot pressing at 580 °C and 45 MPa for 1 h.

and/or b) segregation of molten phase due to capillary effect of the
powder preform.
The ultimate goal of fabrication is to uniformly incorporate GNPs –
achieving greater reinforcing efficiency, ultrahigh reinforcement
strength- within different metal matrices to improve the mechanical
properties of composites for potential engineering applications.
Graphene nanoplatelets have been incorporated as reinforcement by
PM in different metal matrices such as Al, Cu, and Mg to enhance their
mechanical properties. The performance of these composites as well as
fabrication process have been summarised in Table 1 by evaluation of
their mechanical properties in terms of hardness, compressive strength,
Young’s modulus, failure strain, flexural strength (a measure of mate-
rial’s resistance to deformation under bending moment), yield strength,
and tensile strength/ultimate tensile strength.
As can be seen from Table 1 a large number of experiments focused
on the incorporation of graphene into metal matrices using PM ap-
proach, and it is not possible to discuss them all in details. For this
reason and taking into account that the ultimate goal is enhancement of
the mechanical properties of the final composite, the methods with the
highest improvement of mechanical properties among each metal ma-
trix will be discussed critically. In this regard, advantages and drawback
of such methods will be highlighted. Considering Al/GNPs from
Table 1, the highest improvement of 138% in hardness over pure Al
achieved with addition of 1.0 vol-% GNP to Al matrix and 5 h milling
time followed with 2 h sintering time [67]. Increment in hardness of the
Al/GNPs composite was due to proper dispersion, good mechanical
bonding, and formation of Al3C4 [67]. It was also reported that the
milling time plays an important role in hardness of the composite [67].
As indicated by the Raman spectra of the composite (Fig. 11), the in-
tensity of the peaks is reduced with increase of milling time – indication
of particle size reduction [67]. The Scanning electron microscopy
(SEM) micrographs in Fig. 12 confirm the Raman results where more
uniform and smaller particles are resulted after 5 h milling. It was re-
ported by the authors that reduction in Raman intensity was attributed
to amorphization (disorder) of GNPs as a function of milling time
(Fig. 12) [67]. However, there is no explanation on how amorphous
structure forms as a result of breaking the graphene particles. It is be-
lieved this is mainly due to reduction of graphene sheets size and there
are no changes in the crystallinity of graphene. Besides that, the for-
mation of Al3C4 as a hard phase (observed by XRD results) could con-
tribute to increasing the composite hardness. This can be a consequence
of composite process and higher sintering temperature [63,67]. Al-
though it has been suggested that the increase of milling time effec-
tively reduced the size of graphene sheets, promoting defects and da-
mages to the surface of graphene is the drawback of longer milling
times.
From Table 1, the highest improvement of yield strength (84.5%)
and tensile strength (54.8%) of Al-GNP composites obtained by SPS
route [56]. One reason can be explained by applying ultrasonication
technique instead of ball milling for dispersion of powders. Although
ball milling has been an effective approach to reduce the problem of
agglomeration in metal matrices, milling conditions may cause struc-
tural defects, and loss of structural integrity [62,66,68–70]. These de-
fects can trigger carbide formation during subsequent fabrication steps
which may be in favour or unfavourably affect the final nanocomposite
properties [56]. In the study by Bisht et al. [56] GNPs dispersed uni-
formly in aluminum matrix by ultrasonication, and without damages on
GNP surfaces. The second reason for enhanced mechanical properties of
Al/GNPs composite can be attributed to the consolidation process i.e.
SPS [56]. The advantages of this technique over conventional hot
pressing is applying relatively lower temperature and shorter sintering
time for densification and heating [71–73]. SPS induces greater density
solely due to its mode of heating and joining the powder particles (still
not fully understood as how the plasma works in powder preforms), the
shorter heating time and lower temperatures countering any possible
grain growth during sintering [73]. SEM images (Fig. 13) confirmed no
sign of damages on GNP surfaces during high power sonication and SPS
process [56].
Finally, the strength of composite was dependant on the percentage
of GNPs where the highest yield strength and tensile strength obtained

13
H. Ghodrati and R. Ghomashchi
Fig. 21. Schematic representation for synthesis of GNPs-Ni reinforcement phase
via in situ chemical reduction and GNPs-Ni/Cu composite; a) flake graphite, b)
Hummer’s method to produce Graphene Oxide (GO) nano sheets, c) Addition of
NiSO4·6H2O into GO suspension to synthesize GO nanosheets-Ni2+, d) GNPs-Ni
reinforcement phase by reduction of GO nanosheets-Ni2+ with N2H4·H2O, e and
f) mixing GNPs-Ni and Cu powders by ultrasonication technique (wet mixing),
g) bulk GNPs–Ni/Cu composites consolidated by SPS [91].
for 1% wt GNPs content [56]. As can be seen from Fig. 13, 3 and 5 wt%
GNP led to agglomeration and non-uniform grain size distribution with
similar average grain size to the larger grains of Al [56]. A uniform
grain size distribution and restricted grain growth achieved by GNPs up
to 1% wt during sintering [56]. In addition to homogeneous grain size
distribution, the microstructure analysis of Al/Gr composite (Fig. 14)
revealed clear interfaces devoid of carbide formation and impurities
[56]. Therefore, well-distributed GNP in the Al matrix along with good
interfacial bonding increased mechanical properties of the Al/GNP
composite [56]. On the other hand, as discussed earlier, graphene and
Al form a weak physisorption interface, and thus the mechanical
properties may not improve significantly. In order to increase inter-
facial bonding and so as the mechanical properties, graphene can be
coated by metals such as Ni, Co, and Ti prior to mixing with Al matrix.
As such chemisorption interfaces form stronger bonding than physi-
sorption ones, and this might be a promising strategy of strongly
bonded interfaces. The novel approaches in regards to coating graphene
with metallic particles will be discussed later.
For Cu/GNPs composites reported in Table 1, homogeneous dis-
persion of 8 vol% GNP content within the Cu matrix resulted in the
14
FlatChem 16 (2019) 100113
highest increase of yield strength by 114% and Young’s modulus by
37% over pure Cu [66]. This is attributed to the uniform distribution of
GNPs and grain refinement [66]. In this study, there was no detectable
amount of carbide formation based on XRD results. Similar to Al-GNP
composites, GNPs tend to agglomerate at higher concentrations ( 8 vol-
% GNP) [66]. Thus, such yield strength and Young’s modulus obtained
with GNP contents less than 8 vol-% GNP (Fig. 15) [66]. However,
according to Raman spectra in Fig. 16, the ID/IG ratio of milled GNPs
increased comparing to the pristine GNPs [66]. The increase of ID/IG
ratio is indicative of promoting defects in GNPs arising from the re-
peated deformation, cold welding and fracturing actions of the ball
milling process [66,74]. This may lead to some damage of the surfaces
and edges of the GNPs and reduction of the mechanical properties of
final composite [66].
As for Mg/GNP composites obtained by PM route (Table 1), the
highest improvement in hardness (∼42%), elastic modulus (89%),
yield strength (117%), ultimate tensile strength (58%), and failure
strain (96%) achieved with 0.54 vol-% GNP over monolithic Mg [75].
Due to heat production during ball milling, Mg powder may be burnt
easily. Thus, Rashad et al. [75], mixed powders in a solvent by me-
chanical agitator instead of ball milling. Besides that, mechanical
properties of Mg in this experiment improved with hybrid Cu–GNPs
reinforcement [75]. As can be seen from optical micrographs in Fig. 17,
the grain size reduced with increase of the GNPs content. It was con-
firmed by microstructural analysis in Fig. 18 that presence of the second
phase (Mg2Cu intermetallic phase) observed due to limited solubility of
Cu in Mg [75]. The intermetallic phases precipitated during sintering
process pinned down the grain boundaries and inhibited grain growth
[75]. Also, the SEM images in Fig. 18 confirm the GNPs are well em-
bedded within the Mg matrix ensuring the absence of defects [75]. The
good interfacial bonding between Cu-GNP reinforcement and Mg was
confirmed by TEM images in Fig. 19. As can be seen, the intermetallic
phase of Mg2Cu is well-bonded with the Mg matrix ensuring efficient
load transfer [75] in confirmation with previous reports [76,77]. Si-
milar to Al/Gr interface, Mg may form weakly physisorbed interface,
and in order to improve interfacial bonding and so as dispersion, gra-
phene can be decorated with strongly chemisorbed metallic particles
(i.e. Ni, Co, and Ti) before mixing with Mg. Such novel methods have
been discussed in the next section.
As discussed milling time [62,67,69,78], GNP concentration
[56,61,64,66,67,69,75,77,79,80], and sintering conditions [67] are
critical to mechanical properties of the composites reinforced with
graphene nanosheets. In this regard, it has been shown that GNPs form
clusters as a consequence of short milling time, or promote disordering
and defects with further increase of milling time [62,67,69,78]. Hence,
during ball milling the surface and edges of GNPs can be damaged
leading to decline of mechanical properties of the composite
[67,69,70,76]. The defect formation during milling can promote for-
mation of carbides at higher sintering temperature as reported for
carbon nano-tubes [81–85]. The defects are expected to increase dif-
fusion rate, a pre-requisite for the formation of carbides in Al-C (Al4C3)
composites. Apart from milling effect, uniform dispersion of GNPs be-
comes more difficult by increasing its concentration in the metal matrix
[65,66,86,87]. The increased amount of GNP cause agglomeration, and
degrading the strength of composites [65–67,69,86,87]. As for sintering
conditions, higher sintering temperatures result in higher diffusion
rates which may cause better consolidation and interfacial bonding
between GNP and matrix. On the other hand, it may lead to the for-
mation of brittle carbide at the interface, and decreasing hardness and
strength of the composite [63]. Thus, to achieve a high performance
composite, it is extremely important to uniformly distribute graphene in
the metal matrix having clean and strong interface, without
H. Ghodrati and R. Ghomashchi
agglomeration and defect sites. Despite improvement in mechanical
properties of composites through powder metallurgy, it is still re-
markably lower than predicted values for GNPs having tensile strength
of ∼125 GPa and elastic modulus of ∼1.0 TPa [66]. As such, there has
been a comparison between experimental and theoretical calculations
of Young’s moduli for GNP/Cu (Fig. 20). As can be seen from Fig. 20,
there is a gap between predicted and experimental results. This suggests
optimization of processing, improving distribution of GNP in metal
matrix, and enhancing interfacial bonding at the interface are essential
[66].
Overall, uniform dispersion of graphene reinforcement in the metal
matrix is necessary, and conventional processing methods have not
been able to effectively incorporate graphene into metal matrix [88].
This difficulty is associated with high specific area and van der Waals
interactions between graphene sheets which promote agglomeration
[88]. In addition to clusters, relatively high processing temperature
techniques (general sintering and melting process) are not applicable
because graphene is easily decomposed and damaged or bulk amount of
unfavourable interfacial reaction product might form during sintering
(e.g. Al4C3) [88]. Therefore new approaches are required to improve
uniform dispersion of graphene into metal matrix as well as enhancing
interfacial bonding.
5. Novel methods
5.1. Coating graphene
Recently, there has been interest in coating graphene reinforcement
with metallic nanoparticles prior to consolidation. This alternative ap-
proach provides uniform dispersion and efficient graphene-metal in-
terfacial bonding by increasing the adhesion contact points on the
surface of graphene [89]. In this concept, decoration or coating the
surface of either reduced graphene oxide (RGO) [89–93] or pristine
GNPs [60,94] has been obtained by metallic nanoparticles. This
15
FlatChem 16 (2019) 100113
Fig. 22. SEM images of a)Cu and b)1.0 vol%
GNPs–Ni/Cu composites showing the GNPs (white
phase) are uniformly dispersed in the matrix (grey
phase) without agglomeration, and fracture surfaces
of c) Cu and d) 1.0 vol% GNPs–Ni/Cu composites
showing GNPs are tightly embedded in the Cu matrix
(marked by arrows) [91].
deposition on the surface of the RGO or pristine GNPs occurred by
electroless plating [89,90,94], in situ chemical reduction [91], mole-
cular level mixing [92], thermal annealing [93], and chemical vapour
deposition [60]. In such studies listed in Table 2, mechanical properties
enhanced due to well dispersed and strongly bonded GNPs with the
metal matrix [60,89–94]. The uniform distribution of GNPs in the
matrix achieved through the attached nanoparticles on the surface and
embedded between neighbouring graphene nanosheets which acted as
spacers to restrict graphene from agglomeration [60,89–94]. Also, a
stronger interfacial bonding at the interface achieved through chemi-
sorbed metallic particles. In addition to either phsysisorbed or chemi-
sorbed metallic particles, strong covalent interaction between oxygen
mediated graphene and Cu or Ni at the interface facilitated better
bonding and thus effective stress transfer from metal matrix to the re-
inforcement [60,89–94].
Considering Cu matrix in Table 2, metallic particles of Ni and Cu
have been used to coat RGO by electroless plating [89,90] and in situ
chemical reduction [91]. Moreover, in-situ growth of Mo2C nano-
particles on RGO through thermal annealing applied to produce Mo2C@
RGO/Cu composite where yield strength increased largely by 127%
comparing to pure Cu [93]. Likewise, in situ chemical reduction ap-
proach has shown significantly improved Young’s modulus by 61% and
yield strength by 94% through addition of only 1.0 vol% GNSs (1.88 vol
% GNSs-Ni) [91]. The advantage of this approach is its simplicity and
using less chemicals comparing to electroless plating method. A sche-
matic representation of this approach has been demonstrated in Fig. 21.
SEM images in Fig. 22, revealed homogeneous distribution of GNPs in
the Cu matrix due to decoration of the GNPs with Ni nanoparticles.
Besides that, good interfacial bonding without pores and cracks ob-
served in the fracture surface of the composite (Fig. 22(d)).
Regarding the surface treatment of reduced graphene oxide by
electroless plating and in situ chemical reduction methods, the strong
interfacial bonding between the GNPs and Cu matrix occurred due to
the oxygen-mediated bonding [89–91]. For instance, the presence of
H. Ghodrati and R. Ghomashchi
Fig. 23. a) TEM image of the GNP/Cu composites, and corresponding EDS analysis for the element distribution at b) region A (interface), c) region B (Cu), d) C
(GNPs); e) schematic representation of oxygen mediated bonding at the interface of the GNP and the Cu matrix [90].
such bonding has been confirmed in Fig. 23 through TEM images and
corresponding EDS analysis [90]. As can be seen from Fig. 23, the GNP/
Cu interface (region A) has highly concentrated oxygen element as
compared to the Cu matrix (region B) and GNP (region C) [90]. On the
other hand, there are some disadvantages of using reduced graphene
oxide as reinforcement phase. Production of RGO not only consumes
large amount of chemicals but also introduces structural defects as a
consequence of reducing graphene oxide (GO) [93]. The structural
defects of RGO and GO degrade the strengthening efficiency of gra-
phene [60]. Therefore, coating pristine graphene can be an alternative
approach in terms of cost-effectiveness and preservation of structural
strength of GNPs. In this regard, electroless Cu and Ni plating applied to
deposit these metallic nanoparticles on the surface of GNPs before
consolidation process [93]. The yield strength of the GNP/Cu compo-
sites improved by 64.5% with addition of 0.5 vol-% GNP-Ni and 49.1%
with 0.5 vol-% GNP-Cu [93]. Although these improvements are not as
16
FlatChem 16 (2019) 100113
much as previous methods (Table 1), new approaches benefit from
overcoming problems of structural defects and damages during redu-
cing graphene oxide and ball milling.
Furthermore, new methods including molecular level mixing [92]
and in situ chemical vapour deposition (CVD) [60] have been used to
anchor the surface of graphene nanosheets with metallic nanoparticles
prior to mixing with Al matrix. Decoration of GNPs with metallic par-
ticles resulted in uniform dispersion by preventing clustering of GNPs
and also strong interfacial bonding through forming intermetallic
compounds at the interface [60,92]. Thus, synergistic effect of disper-
sion strengthening and better stress transfer led to improvement in
tensile strength and hardness by 77.5% and 29.1%, respectively, which
obtained by molecular level mixing [92]. As for CVD method, the same
mechanisms increased tensile strength by 30% and yield strength by
75% [60]. As mentioned above, reducing graphene oxide and ball
milling cause defects and damages to the surface of GNPs. This might be
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Fig. 24. Schematic representation of producing GNS/Cu composite [97].

Fig. 25. SEM images of the fracture surface of composite GNS/Cu prepared by SPS. GNP contents with a) 10 vol% b) 20 vol% and c) and d) 30 vol% [97].

two main reasons that mechanical properties of composites have not systematic study. Finally, sintering conditions including time, tem-
significantly improved through these methods [60,92]. perature, and pressure should be studied to reach the ultimate goal of
Decoration of graphene nanosheets with metallic nanoparticles is at well distributed graphene and increased interfacial bonding.
its early stage of development and there still remain rooms for im-
provement. Damage of GNPs during milling time is inevitable and thus
5.2. Vacuum filtration
alternative methods should be developed to efficiently eliminate ball
milling from fabrication process of composite. For instance, functio-
Vacuum filtration applied to overcome the difficulties of dispersion
nalizing Al matrix with Cu nanoparticles prior to consolidation sig-
in graphene-reinforced metals by [96–98]. As demonstrated in Fig. 24,
nificantly improved tensile strength by ∼200% compared to un-
two steps of vacuum filtration and spark plasma sintering (SPS) em-
reinforced Al [95]. This was achieved by in situ CVD [95]. Furthermore,
ployed to fabricate well-aligned graphene in the GNS/Cu composite
the optimal concentration of metallic nanoparticles decorating gra-
[98].
phene nanosheets, as well as GNPs can be obtained through a
The novelty of this approach is that graphene is not randomly

17
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Fig. 26. a) Tensile stress–strain curves for different content of GNPs, and b) tensile strength (σb) and elongation (δ) for pure Cu and different amount of graphene in
GNP/Cu composite with the load parallel and perpendicular to the alignment direction [98].

Fig. 27. a) TEM image of the interface for RGO/CuCr composite, b) HAADF-STEM image (high angle annular dark field -scanning transmission electron microscopy)
at the interface, and c) corresponding analysis of the CuCr-RGO interface. The presence of Cr at the interface is clear from the Cr signal, which intensified in the
interface region due to carbide formation [100].

distributed in the composite in contrast to the previous studies. For
instance, it is clear from Fig. 25 that GNSs are almost aligned hor-
izontally and the GNSs contents have no effect on the orientation [97].
However, the incorporation of well-aligned GNPs resulted in aniso-
tropic mechanical properties [98]. The anisotropic mechanical prop-
erties of the composite investigated along the in-plane and through
plane directions [98]. Although the tensile strength moderately in-
creased with in-plane direction (26% at 10 vol% GNPs), they were
considerably higher than those of through plane [98]. Likewise, the
elongation along the in-plane direction was significantly higher than
that of the through-plane (Fig. 26).
The advantage of this method is that highly aligned GNSs in the
composite obtained regardless of the content of graphene. In conven-
tional methods, the concentration of graphene in the metal matrix
cannot increase due to the formation of agglomeration. Therefore, va-
cuum filtration paves the way to fabricate graphene-reinforced metal
matrices with higher content of graphene and with lower risk of ag-
glomeration.
5.3. Matrix-alloying
In this novel approach the interface of RGO (reduced graphene
oxide)/metal matrix optimized by in-situ formation of Ti carbide
(Ti8C5) [99] and Cr carbide (Cr7C3) [100]. The composites generated

18
H. Ghodrati and R. Ghomashchi
Fig. 28. Schematic representation of plasma treatment to create defects on the surface of GO (P-GO) following by thermal reduction and SPS to fabricate P-RGO/Cu
composite [102].
via flake powder metallurgy and followed by SPS [99,100]. Considering
the weak interaction between Cu and graphene, the interfacial bonding
improved by the formation of such carbides. This interfacial design
resulted in considerable increase of the mechanical properties of final
composites [99,100]. For instance, the tensile strength of RGO/CuTi
increased by 20.2% compared to the RGO/Cu [99]. Comparing the
yield strength and tensile strength of CuTi alloy with those of RGO/
CuTi composite, they enhanced considerably to 106.2% and 57.7%,
respectively [99]. Similarly, the yield strength and ultimate tensile
strength of RGO/CuCr composite increased significantly by 222%
(82%) and 28% (19%) than those of CuCr (RGO/Cu) [100]. This was
due to the dual role of Cr7C3 layers/nanoparticles at the interface
(Fig. 27) to improve the load transfer efficiency and promoting the
dislocation strengthening [100]. The advantage of this approach over
coating is that matrix-alloying is less complex and also does not require
harmful additives or solvents [99]. However, it is important to point out
that the formation of hard and brittle phases at the interface is expected
to affect the composites susceptibility to crack initiation at the interface
and thus reducing the composite toughness.
5.4. Graphene defect engineering via plasma treatment
It is well known that the number of defects at edges of dangling
bonds is considerably higher than those of graphene basal-plane [101].
As we know, the basal-plane occupies larger interface area in the
composite comparing to the edges. Therefore, creating defects on the
surface of graphene by plasma treatment is a novel and efficient way to
19
FlatChem 16 (2019) 100113
enhance interfacial bonding [102,103]. This method as illustrated in
Fig. 28 involves the plasma treatment to create limited number of de-
fects on the surface of GO [102]. The defective sites were ideal platform
for the in situ formation of CuxOy during the sintering process of plasma
treaded graphene (P-RGO/Cu) composite [102].
As illustrated in Fig. 29, the TEM images show a good interfacial
bonding between plasma treated graphene (P-RGO) and Cu matrix
without cracks and voids [102]. Furthermore, according to the HRTEM
images in Fig. 29 CuO, Cu2O, and Cu4O3 coordinated at the interface
[102]. The coordinated CuxOy oxides at the interface, therefore, led to
the higher strength of composite compared to that of untreated GO
(RGO/Cu) [102]. For example, the tensile strength and yield strength of
1 vol% P-RGO/Cu increased nearly 10% and 23% respectively com-
pared to the 1 vol% RGO/Cu composite [102].
The defect engineering also used for the graphene/CuCr composite
[103]. The treated graphene (P-GO) from plasma treatment reinforced
the matrix-alloy of CuCr [103]. Without such treatment, the Cr7C3
carbide formed only at the edge of interface in RGO/CuCr composite.
Plasma treatment led to the formation of carbide on the basal-plane as
well [103]. Therefore, yield strength of 1 vol% P-RGO/CuCr composite
increased 37% in comparison with the 1 vol% RGO/CuCr composite
[103]. Regarding the unreinforced alloy of CuCr, the yield strength
increased by 180% [103]. A schematic representation of defect sites
and interface for both plasma treated and untreated GO displayed in
Fig. 30.
H. Ghodrati and R. Ghomashchi FlatChem 16 (2019) 100113

Fig. 29. Interface analysis of 1 vol% P-RGO/Cu composite. a) and b) TEM images of well-bonded interface without cracks and voids, c) HRTEM image of the selected
area in red square of b. c) HRTEM image of the selected area in red square of a and relevant Fast Fourier transform (FFT) pattern recorded in d1. e) HRTEM image of
composite interfacial area and related FFT patterns recorded in e1, e2, e3 and Inverse Fast Fourier transform (IFFT) image recorded in e4 with high dislocation density
[102].

Fig. 30. a) P-RGO/CuCr interface, and b) RGO/CuCr interface [103].

20
H. Ghodrati and R. Ghomashchi
6. Conclusions
Graphene has unique electronic structure with superior properties
of large aspect ratio, extraordinary Young’s modulus and strength, ex-
cellent electrical and thermal conductivity. Owing to such superb me-
chanical properties, graphene nanosheets have been used as re-
inforcement to enhance mechanical properties of metal-based
composites. In this regard, conventional powder metallurgy has widely
been used to fabricate metal matrix composites reinforced with gra-
phene. It is well established that uniform distribution and strong in-
terfacial bonding are significant factors to have a high performance
composite. Although ball milling has been broadly employed for dis-
persion, there still exist obstacles to have well-distributed graphene in
the matrix without defects and damages to the surface of graphene
sheets. These defects and damages cause decline of mechanical prop-
erties. Thus, it is essentially important to develop new methods to
overcome such challenges. Novel methods including coating graphene,
vacuum filtration, matrix-alloying, and graphene defect engineering via
plasma treatment have shown alternative way to conventional
methods.
Acknowledgement
H. G. gratefully acknowledges the Australian Government Research
Training Program Scholarship for the financial supports. R. G. ac-
knowledges the ARC Research Hub for Graphene Enabled Industry
Transformation at the University of Adelaide.
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