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Experimental investigation of interfaces in

graphene materials/copper composites from a new
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Cite this: RSC Adv., 2016, 6, 52219

perspective
Dan-dan Zhang and Zai-ji Zhan*

Received 23rd March 2016
Accepted 23rd May 2016
DOI: 10.1039/c6ra07606h
www.rsc.org/advances
Copper matrix composites reinforced with three types of graphene materials, namely graphene
nanoplatelets, nickel-plated GNPs and reduced graphene oxide, were separately fabricated using
a molecular-level mixing process. Different from nanoparticles and nanofibers, graphene materials
exhibit a unique two-dimension structure. The interface between graphene and the matrix could be
divided into two types, namely graphene plane–Cu (Dp) and graphene edges–Cu (De). The interface
microstructure between the constituent phases in graphene/Cu composites were observed for the first
time from the two directions by means of transmission electron microscopy (TEM). TEM analysis results
showed a big difference in interface microstructure and bonding mechanism in the three kinds of
composites. The graphene materials were coherently bonded with the copper matrix in terms of
mechanical, metallurgical or chemical bonding.

and surface modication,32,33 have been developed to uniformly

Introduction
Copper matrix composites are widely used in the microelec-
tronics and automobile industry due to their excellent
comprehensive properties.1–3 Many nanomaterials with
outstanding mechanical and physical properties have been
applied as reinforcements to reinforce the copper matrix.4–7
Graphene, a single-layer graphite sheet, has been regarded as
a promising candidate of the next generation reinforcement for
copper matrix composites because of it's big specic
surface area (2630 m2 g
1),8 high thermal conductivity (5  103
W m
1 K
1),9,10 good electrical conductivity (106 S m
1),11 and
exceptional tensile strength (125 GPa).9,12
Graphene can be synthesized by different approaches, such
as mechanical exfoliation,13,14 chemical vapor deposition,11,15–17
chemical reduction18,19 and large-area graphene growth
method.20 The structure of graphene strongly depended on the
synthesized methods, different synthesized method led to the
big difference in structure and properties, which was subsumed
under the concept of “graphene derivatives” or “graphene
materials”. Nickel plated graphene nanoplatelets (Ni-GNPs)
were also mentioned in the literature, therefore, graphene
materials should be incorporated into the matrices through
different methods to achieve good interface bonding and
uniform distribution. Several processing methods, such as
powder metallurgy,21–27 disintegrated melt deposition,28
molecular-level mixing (MLM),29 electrochemical method30,31
State Key Laboratory of Metastable Materials Science & Technology, Yanshan
University, Qinhuangdao 066004, China. E-mail: zjzhan@ysu.edu.cn; Tel: +86 335
8501191
incorporate graphene materials into the metal matrices. So far,
powder metallurgy or disintegrated melt deposition have been
used to incorporate graphene nanoplatelets (GNPs) or ultra-thin
graphite sheets (containing multilayer graphene with thickness
of less than 100 nm) into copper matrix successfully.23,24,28 GNPs
showed a good strengthening efficiency in the composites due
to their excellent mechanical properties. For instance, AZ61-
3GNP composite prepared by disintegrated melt deposition
method showed 26% and 11.7% increase in yield strength and
ultimate tensile strength, compared to monolithic alloy.28 Gra-
phene oxide (GO), containing many hydrophilic functional
groups on graphene layer, was the most widely used as gra-
phene precursor to fabricate composites. GO can be reduced to
graphene (RGO) by chemical or thermal reduction.18,34 It has
been conrmed that solution-based methods were suitable for
synthesizing RGO/Cu composites.25,29–31 RGO/Cu nano-
composites containing 2.5 vol% RGO synthesized by the MLM
method showed a 30% increase in tensile strength and a 30%
increase in elastic modulus compared with pure copper.29
Moreover, graphene plated with metal nanoparticles has been
incorporated into metal matrices to enhance the weak interface
of graphene/metal composites made by powder metallurgy. The
copper composites with only 1.0 vol% Ni-graphene showed
a 61% increase in elastic modulus and a 94% increase in yield
strength.33
Graphene materials have showed excellent strengthening
effect in copper matrix composites. Strengthening mechanisms
included grain-size renement, Orowan strengthening, load
transfer effects as well as thermal expansion mismatch. The
interface bonding strength between graphene materials and

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matrix in graphene/Cu composites may vary due to the different

fabrication methods as well as different strengthening mecha-
nisms. So far, the main efforts have been focused on developing
new processing route to disperse graphene homogeneously into
matrices and enhance the interface bonding between the
constituent phases in composites. To understand the graphene/
matrix interface structure is still necessary in order to provide
the fundamental knowledge of controlling the microstructure,
so as to optimize the preparation methods and parameters.
Some interface bonding types presented between graphene
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materials and the metal matrices were mentioned in the pub-

lished papers. For example, mechanical bonding usually existed
in GNPs/copper composites fabricated by ball milling due to the
non-wetting of the GNPs and matrix.24 Oxygen-mediated
bonding was deduced in oxygen-containing graphene mate-
rials reinforced copper or nickel matrix composites.35,36
The present study is undertaken in an effort to understand the
interface microstructure of graphene materials/Cu composites by
means of transmission electron microscopy (TEM). Copper
matrix composites reinforced with GNPs, Ni-GNPs and RGO were
separately fabricated using a MLM process. The purposes of this
work are twofold: rstly, to observe the interface microstructure
between graphene and Cu from two directions since graphene
has a typical two-dimension structure, namely graphene plane–
Cu and graphene edges–Cu, which were hereaer called the Dp
and De; secondly, to understand the interface structure and
strengthening mechanisms of constituent phases in graphene
materials/Cu composites.
Experimental
Sample preparation
As-received raw materials were used in the present work. The
GNPs purchased from XFNANO Material Technology Co., Ltd.
were 98.9% in purity (1.1 wt% O) and 1–5 mm in lateral
dimension. The thickness of raw GNPs was 5–10 nm, corre-
sponding to approximately 15–30 layers of monolayer gra-
phene.23 Ni-GNPs were synthesized by a typical electroless
nickel plating process. The GNPs were rst concussed by
ultrasonication (100 W) for 2 h in deionized water. Then the
GNPs were immersed in 200 ml of SnCl2 solution (10 g l
1 SnCl2,
40 ml l
1 HCl) under ultrasonication for 30 min for sensitiza-
tion. Aer being washed and ltered with deionized water, the
sensitized GNPs were put into 200 ml of PdCl2 solution (0.5 g l
1
PdCl2, 25 ml l
1 HCl) under ultrasonication for another 30 min.
The activated GNPs were added into the solution of NiSO4$6H2O
(0.076 mol l
1), NaH2PO2$H2O (0.283 mol l
1), Na3C6H5O7$2H2O
(0.034 mol l
1), NH3$H2O (keep the pH value at 8.75) to
complete Ni plating at a water-bath temperature of 35  C. The GO
aqueous solution with concentration of 2.86 mg ml
1 was
purchased from JCNANO Material Technology Co., Ltd. The GO
was $99% in purity, 1–5 mm in lateral dimension, 0.8–1.2 nm in
thickness and $99% in single layer ratio. Cu(CH3COO)2$2H2O
used as precursor of Cu was in analytically pure grade. Fig. 1
showed the representative morphology of GNPs, Ni-GNPs and
GO powders. The X-ray photoelectron spectra (XPS) of raw
powders shown in Fig. 1(a)–(c) were given on the right. Fig. 1(a)
Fig. 1 SEM micrographs of GNPs (a) and Ni-GNPs (b); TEM image of
GO powders (c). The images on the right are the XPS spectra of
powders in (a–c).
showed the morphology of GNPs that exhibited a stacking ake
structure, suggesting ultrasonic pre-treatment was necessary to
overcome the attraction between graphene layers. Fig. 1(b)
presented that the Ni-GNPs exhibited ake shape aer
electroless nickel plating. The coating layer was dense and
smooth. Fig. 1(c) showed that GO powder exhibited an ultra-
thin ake structure.
The GNPs/Cu composite powders with GNPs content at
0.5 vol% were synthesized by a MLM process. Steps involved in
the MLM method were as described in the previous study.37 The
sensitization and activation process was not performed during
the preparation of Ni-GNPs/Cu and RGO/Cu composite powders.
The as-prepared graphene materials/Cu composite powders
were consolidated into bulk nanocomposites with full densi-
cation by spark plasma sintering (SPS), which could provide high
heating rate and rapid consolidation through high-joule heating
and spark plasma generated between the powders. The
composite powders were sintered at 600  C for 5 min with
a heating rate of 50  C min under a uniaxial pressure of 45 MPa.
Characterization
The microstructure of the raw materials and composite powders
was examined using a scanning electronic microscopy (SEM)
and TEM, both of which were equipped with energy-dispersive
X-ray spectroscopy (EDS) system. The powders were fully
dispersed in ethanol using an ultrasonic oscillator and then
collected on a 200-mesh copper grid to make powder TEM
samples. The collected powders were thin enough to be
observed by TEM at 200 kV. XPS and Raman spectroscopy were

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Fig. 2A schematic diagram of the TEM observation directions of Dp
and De (a); the dimensions (in mm) of tensile samples (b).
applied to investigate the chemical composition and charac-
terize the structure of graphene materials. Interface micro-
structure of the bulk composites was also characterized by TEM.
TEM samples of the bulk composites were rstly mechanically
polished and then thinned to 20 mm by mechanical polishing,
followed by ion milling. Fig. 2 showed the schematic diagram of
the TEM observation directions of Dp and De. The mechanical
properties of the composites were characterized by tensile tests.
Tensile tests were conducted at ambient temperature (25  C) on
a universal testing machine (TH5000) with the crosshead speed
of 0.6 mm min
1. The test samples with a gauge length of 10
mm and cross-section of 2 mm  1.5 mm were machined from
the sintered billets. Three samples were tested from each sin-
tered billet for tensile tests to minimize the error. The average
tensile strength, yield strength (0.2%) and total elongation were
determined from the tensile curves.
Results and discussion
Fig. 3 showed the typical SEM micrographs and Raman spectra
of elemental powders aer reduction by high purity hydrogen
(MLM process). Graphene materials could be identied from
the composite powders (Fig. 3) based on their unique
Fig. 3 SEM micrographs of GNPs/Cu (a), Ni-GNPs/Cu (b) and RGO/Cu
(c) composite powders; (d) Raman spectra of activated GNPs, GNPs/
Cu, Ni-GNPs/Cu, GO and RGO/Cu powders. The insets are the EDS
corresponding to the marked points.
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appearance. The existence of graphene materials indicated little
decomposition or damage of graphene structure was made
during the MLM process, which was further proved by Raman
analysis below. Fig. 3(a) presented the morphology of GNPs/Cu
composite powders. The GNPs were subtranslucent and did not
aggregated obviously in copper particles. However, the GNPs
showed a lateral size of 20–30 mm, which was 4–6 times as large
as raw material. It might be caused by that edges of some
multilayer graphene adsorbed on the in-plane of another gra-
phene resulting an increase of lateral size but no obvious
increase in thickness was observed. Meanwhile, some copper
particles were adsorbed on the surface of GNPs as shown in
Fig. 3(a). The adsorbed particles inhibited the aggregation of
GNPs and would improve wettability between these constituent
phases leading to good interface bonding of sintered compos-
ites. Fig. 3(b) and (c) showed the morphology of the Ni-GNPs/Cu
and RGO/Cu composite powders. Agglomerate of Ni-GNPs or
RGO could hardly be seen. Importantly, the Ni-GNPs were well
wetted by the copper particles, proving that the plated Ni
successfully decreased the contact angle of copper on the GNPs.
Raman spectroscopy of the raw and composite powders char-
acterized the structure change of graphene materials, as shown
in Fig. 3(d). Raman spectra of the GNPs/Cu and Ni-GNPs/Cu
powders showed typical characteristic peaks of GNPs, while
the Raman spectra of the RGO/Cu powders were the signatures
of GO structure, insulating that main graphene structure was
maintained during the MLM process. It could be obviously
found that GO and RGO were more defective compared with
GNPs materials based on the intensity ratio of the D band to G
band, ID/IG. Moreover, G bands of GO showed right shi
compared with G bands of GNPs, indicating that RGO exhibited
fewer graphene layers than that of GNPs.38
The interfacial bonding played a key role in the load transfer
between the matrix and graphene, as well as in the inhibition of
dislocation movement, which are the most important
strengthening mechanisms of graphene/metal composites.39
The following sections focused on the discussion of the inter-
face microstructure between the three types of graphene
materials and the copper matrix.
Interfaces in GNPs/Cu composites
The distribution feature of GNPs in the composites was char-
acterized by TEM, as shown in Fig. 4. According to the selection
Fig. 4 TEM micrographs of GNPs/Cu at low magnification.
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of electron diffraction pattern (inset in Fig. 4(a)), the light-
colored phase was GNPs, while the dark phase was the copper
matrix. The GNPs located either at grain boundaries or in grain
interiors of the copper matrix. As shown in Fig. 4(a), the GNPs
with diameters of below 1 mm distributed at the copper grain
boundaries, which maintained the ake structure like the raw
powder. The GNPs in grain interiors were spherical in shape
with size of several decades nanometers, as shown in Fig. 4(b).
The special distribution was attributed to the separation of ne
graphene pieces from raw GNPs during the ultrasonic oscilla-
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tion and mechanical stirring process in MLM method.
Fig. 5 showed high resolution transmission electron
microscopy (HRTEM) images and schematic diagrams of the
interface between GNPs and Cu in directions of Dp and De. The
GNPs in Fig. 5(a) were about 1 mm in lateral dimension and
about 30 nm in thickness. Fig. 5(a) presented a bright-eld TEM
image of the interface between GNPs basal plane and the copper
matrix in Dp. The interface was free of voids, gaps or impurities,
which was further illustrated in Fig. 5(c), a HRTEM image taken
from the marked area in Fig. 5(a). The graphene layers were
clearly stacked and the spaces between lines were about 0.34
nm, close to the theoretical value for graphene stacking. As
shown in Fig. 5(c), the interface between GNPs and the copper
Fig. 5 Interface TEM and HRTEM micrographs of the GNPs/Cu
composite in Dp (a and c) and in De (b and d); interface schematic
diagrams in Dp (e) and De (f).
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matrix was clean and well bonded, illustrating a mechanical
bonding. There was a 2 nm wide step at the interface. The
uneven interface could provide a mechanical lock between
GNPs and the copper matrix. The interface microstructure in De
was shown in Fig. 5(b) and (d). The le image in Fig. 5(d) was
a HRTEM image taken from the interface of marked area in
Fig. 5(b), while the right one corresponded to the surface of
GNPs in the marked area. It was also clear that the GNPs edges
were coherently bonded with the copper matrix without voids or
gaps. Different from Dp, the interface in De was uneven and the
two phases were interdigitated at an atomic scale, which was
estimated as metallurgical bonding.40 The cause of the interfa-
cial difference in the Dp and De might be that the carbon atoms
at graphene edges differed from those away from the edges.
There are many dangling bonds and vacancies at graphene
edges, and the uneven edges were observed using annular dark
eld of a low-voltage scanning transmission electron micro-
scope.41 During the decomposition and reduction of copper
acetate, Cu atoms coherently grew on the uneven graphene
edges, resulting atomic-scale diffusion at the interface. More-
over, the localized plasma heating might also promote this
quite low diffusion when the green body underwent through
SPS.29 Some copper oxides nanoparticles were observed on the
surface of GNPs, as shown in Fig. 5(d). The formation of copper
oxides was mainly attributed to the reaction between the copper
reduced from copper acetate and native oxygen of raw GNPs.
These oxides complicated the interfacial microstructure. The
existence of native oxygen on GNPs offered numerous sites of
oxygen-mediated bonding which could enhance the interfacial
bonding.29,35,36 The formation of copper oxides would reduce the
oxygen-mediated bonding, leading to a decrease of interface
bonding strength. Based on the observation result, schematic
diagrams in Dp and De of the GNPs/Cu composite were illus-
trated in Fig. 5(e) and (f). The interfacial bonding of GNPs/Cu
fabricated by MLM was a combination of mechanical bonding
(Dp) and metallurgical bonding (De). Normally, the metallur-
gical bonding was not seen in the interaction between GNPs and
the copper matrix.24
Interface investigation of Ni-GNPs/Cu composites
Fig. 6 showed low-magnication TEM micrographs of Ni-GNPs/
Cu composites. Ni-GNPs distributed both at grain boundaries
and grain interiors of the copper matrix. As shown in Fig. 6(a),
Fig. 6 TEM micrographs of Ni-GNPs/Cu at low magnification.
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the Ni-GNPs at grain boundaries were about 1 mm in diameter,
which was in accordance with raw GNPs. Ni-GNPs distributed in
grain interiors presented irregular ake shape (Fig. 4(d)), which
was different from GNPs. It might be because of the reduction of
surface tension of GNPs aer the electroless nickel plating.
Fig. 7 showed HRTEM images and typical EDS of the inter-
face of Ni-GNPs/Cu composite. The insets were the diffraction
patterns derived from the Fast-Fourier Transform (FFT) corre-
sponding to Fig. 7(c) and (d). The interfacial microstructure in
Dp was shown in Fig. 7(a) and (c), while the one in De was shown
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in Fig. 7(b) and (d). The Ni-GNPs in Fig. 7(a) were about 250 nm
in lateral dimension and about 40 nm in thickness. As shown in
Fig. 7, the interface between Ni-GNPs and the copper matrix was
coherently bonded without any cracks or voids. Unlike the
interfacial microstructure in the GNPs/Cu composite, a narrow
transition zone of about 1 nm was found between Ni-GNPs and
the copper matrix (Fig. 7(c) and (d)). The results of FFT
diffraction patterns and EDS (Fig. 7(e)–(g)) proved that the
interface transition zone was a layer of nickel. As reported,
electroless plating could improve the wettability between gra-
phene and the copper matrix.32 The nickel particles adsorbed on
GNPs partially dissolved in the copper matrix near the interface,
as shown in Fig. 7(d) and (g). Thus, a good chemical bonding
formed both in Dp and De aer decorating GNPs with nickel
particles. It should be noticed that the proportion of interface in
De was much smaller compared with the one in Dp.
Fig. 7 HRTEM micrographs of the Ni-GNPs/Cu composite in Dp (a and
c) and De (b and d); EDS (e–g) of points marked in (b). The insets are the
diffraction patterns derived from the Fast-Fourier Transform (FFT)
corresponding to the selected regions.
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Consequently, the improvement of interfacial bonding in Dp
highly enhanced the strengthening effect of GNPs. That is,
chemical bonding between Ni-GNPs and the copper matrix
could withstand higher load capacities compared with the
mechanical and metallurgical bonding between GNPs and the
matrix.
Interface investigation of RGO/Cu composites
Fig. 8 showed the distribution of RGO in the copper matrix. Like
GNPs and Ni-GNPs, RGO also distributed both at grain
boundaries and grain interiors of the copper matrix. As shown
in Fig. 8(a), the size of RGO at grain boundaries was rather
smaller compared with GNPs and Ni-GNPs. This mainly
beneted from small thickness of GO and the inhibition of
agglomeration by polar groups on the surface of GO. The ultra-
thin structure of RGO made the TEM interface observation of
RGO/metal composites difficult. Although interfacial structure
of RGO/metal composites has been mentioned, very few
HRTEM images of interface between RGO and metal matrices
have been presented.23,42,43
The morphology of RGO embedded in the copper matrix and
interface microstructure of RGO/Cu were shown in Fig. 9. The
RGO in Fig. 9(a) was about 100 nm in lateral dimension.
Fig. 9(a) presented a bright-eld TEM image of the RGO–Cu
interface in Dp. Thin graphene layers in the middle were etched
off under the exposure of high-voltage TEM electron beam. The
remained RGO was still bonded tightly with the copper matrix.
It demonstrated the interface bonding between RGO and Cu
was stronger than the bonding of graphene interlayers. Fig. 9(b)
showed a bright-eld TEM image of the RGO–Cu interface in De.
The diffraction pattern corresponding to the selected region in
Fig. 9(b) displayed the hexagonal lattice structure of graphene
layer as well as the structure of the copper matrix. RGO was
bonded tightly with the matrix. Fig. 9(c) showed both sides of
a sandwich structure of Cu–RGO–Cu selected in Fig. 9(a). The
thickness of the multilayer RGO was about 10–15 nm, corre-
sponding to 30–50 graphene layers. The coherently bonded
interface was free of voids and gaps. Compared with the
microstructure of GNPs/Cu composite, the interface in Dp
between RGO and the copper matrix was blurry (right in
Fig. 9(c)), which was inferred as a transition zone.44 The blurry
interface indicated interaction between atoms of carbon and
copper. Fig. 9(d) showed that the interface in De of RGO/Cu
Fig. 8 TEM micrographs of RGO/Cu at low magnification.
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Fig. 10 Tensile strength of the composites and pure copper.

aer adding 0.5 vol% GNPs. When using 0.5 vol% Ni-GNPs as
reinforcement instead of GNPs, the tensile strength of
composite further increased by another 25 MPa. As reported,
strength improvement of metal matrix composites reinforced
by graphene could be attributed to grain-size renement, Oro-
Fig. 9 HRTEM micrographs of the RGO/Cu composite in Dp (a and c) wan strengthening, load transfer effects as well as thermal
and De (b and d); EDS (e–g) of points marked in (b). The inset in (b) is expansion mismatch.23,26 The only difference between GNPs/Cu
the diffraction pattern derived from the FFT corresponding to the and Ni-GNPs/Cu composites was whether electroless nickel
selected region.
plating was performed on the surface of GNPs before MLM
process. As discussed above (Fig. 5 and 7), the interface bonding
between Ni-GNPs and Cu was stronger than that of GNPs-Cu.
composite (rectangular selection in Fig. 9(b)) was roughly the
Good interface bonding lead to excellent load transfer, and
same as that of GNPs/Cu. But there was about a 0.5 nm wide
accordingly the tensile strength improved.
transition zone between RGO and the copper matrix. EDS
As shown in Fig. 10, the tensile strength of 0.5 vol% RGO/Cu
(Fig. 9(e)–(g)) corresponding to the points A, B and C marked in
increased by 22 MPa compared with 0.5 vol% GNPs/Cu
Fig. 9(b) was used to analyze the element distribution near the
composites. Based on the differences in structure, distribu-
interface in De. Fig. 9(e) revealed some oxygen existed on the
tion as well as interface bonding, the strength increase was
RGO surface, indicating the reduction of GO was incomplete.
a comprehensive result of many factors, such as Orowan
Reports on the preparation of RGO and RGO based composites
strengthening, load transfer effects and thermal expansion
showed the complete reduction of GO was difficult and time-
mismatch. Moreover, the improvement of strength of Cu
tested.45 Fig. 9(f) illustrated the RGO–Cu interface was an
composites reinforced with GNPs was achieved at the expense
oxygen-rich area, which was in accordance with the diffraction
of ductility, as shown in Table 1. However, 0.5 vol% RGO/Cu
contrast shown in Fig. 9(d). The oxygen signal was rather weak
composite exhibited ductility as good as pure copper, which
in the copper matrix (Fig. 9(g)). The EDS results suggested the
was in accordance with previous report.46 The behavior might be
oxygen-mediated bonding formed between RGO and the copper
arisen from the wrinkle structure of graphene and good inter-
matrix. Compared with the GNPs/Cu composite, the interaction
face bonding between graphene and the matrix. As shown in
between carbon of RGO (with many oxygen of residue polar
Fig. 5(c), 7(c) and 9(c), carbon layers of RGO showed more
functional group) and copper atoms should be stronger as
oxygen-mediated bonding formed both in Dp and De.29 The
formation of oxygen-mediated bonding helped to improve the Table 1 Tensile property of Cu composites and pure Cu
interface bonding in the RGO/Cu composite, such result has
0.2% yield Tensile Elongation
been also found in the RGO/Cu and RGO/Ni composites fabri-
Materials strength (MPa) strength (MPa) (%) R
cated by other chemical methods.35,36
Cu 136  2.3 226  1.6 24.3  1.2
Mechanical properties analysis 0.5 vol% GNPs/Cu 174  5.5 256  4.3 18.1  3.8 55.9
0.5 vol% Ni-GNPs/Cu 175  8.6 281  5.8 11.9  4.4 57.4
Fig. 10 showed tensile strength of the composites and pure 0.5 vol% RGO/Cu 166  10.5 278  4.7 27.9  3.5 44.1
copper. The tensile strength of pure copper increased by 52 MPa

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obvious wavy structure than that of GNPs. The wrinkled RGO
was straightened during load transfer from the matrix to RGO.
Thus, the ductility of the composite was maintained or even
improved. Strengthening efficiency R is widely used to deter-
mine the strengthening effect of reinforcement on composites,
which can be calculated by equation of R ¼ (sc
sm)/Vfsm,
where sc and sm are the yield strength of composite and matrix
respectively, and Vf is volume fraction of the reinforcement. The
R values of graphene materials on pure copper in the present
work (Table 1) were above 44. The strengthening efficiencies
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were much larger than traditional reinforcements on metal
matrix composites, such as Al2O3, SiC, carbon ber and carbon
nanotube.47 It demonstrated that graphene materials were
promising as reinforcements in copper composites. There are
some reports on interface microstructure between the constit-
uent phases in metal composites reinforced with graphene
materials. For instance, Li et al.40 characterized the interface
microstructure between aluminium and graphene using
HRTEM. Lin et al.43 also investigated the GO–Fe interfacial
structure using HRTEM. The former report focused on the
interface in Dp while the latter focused on the interface in De.
The present work studied the interface microstructure in both
directions (Dp and De) for the rst time, which may provide
some information on the microstructure design of graphene
composites.
Conclusions
Copper matrix composites reinforced with GNPs, Ni-GNPs and
RGO were fabricated by a MLM method respectively. The
interface microstructure was discussed based on the directions
of graphene basal plane–Cu and graphene edges–Cu for the rst
time by the TEM observation. All of the three types of graphene
materials were coherently bonded with the copper matrix
without any cracks or voids. Characteristic dimensions of gra-
phene materials can be determined in Dp. Typically, GNPs were
1 mm in lateral dimension and 30 nm in thickness; Ni-GNPs
were 250–1000 nm in lateral dimension and 40 nm in thick-
ness; RGO was 100 nm in lateral dimension and 10–15 nm in
thickness in the composites. A combination of mechanical
bonding in Dp and metallurgical bonding in De was observed
between GNPs and the copper matrix. Beneting from the
decoration of nickel particles on GNPs, a 1 nm-thick transition
zone containing nickel formed at the interface between Ni-
GNPs and the copper matrix. The good interfacial adhesion
between Ni-GNPs and the matrix was attributed to chemical
interaction both in Dp and De. For the RGO/Cu composite,
a transition zone different from the one at the Ni-GNPs/Cu
interface was characterized to be an oxygen-enriched region.
The interfacial adhesion between RGO and the copper matrix
was oxygen-mediated chemical bonding. The improvement of
interface bonding strength increased tensile strength of
composites containing the same graphene material. The detail
observation of interface microstructure is advantageous to the
interface design of graphene material/Cu composites.
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Acknowledgements
This work was supported by the National Basic Research
Program of China (2010CB71600).
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