Phys. Status Solidi A 211, No. 1, 184–190 (2014) / DOI 10.1002/pssa.

201330051

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applications and materials science
Enhanced strength in bulk
graphene–copper composites
Ke Chu*,1 and Chengchang Jia2
1
School of Mechatronic Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
2
School of Material Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P.R. China

Received 18 June 2013, revised 5 September 2013, accepted 22 September 2013

Published online 31 October 2013

Keywords graphene nanoplatelets, metal–matrix composites, powder metallurgy, yield strength

* Corresponding author: e-mail [email protected], Phone/Fax: þ0931-82345659

Graphene nanoplatelets (GNPs) exhibit ultra-high strength and unreinforced Cu, the GNP/Cu composites showed a remarkable
elastic modulus. Therefore, they are potential ideal reinforcements increase in yield strength and Young’s modulus up to 114 and
in metal–matrix composites (MMCs). In this work, we report the 37% at 8 vol.% GNP content, respectively. The extraordinary
use of GNPs to strengthen the bulk Cu-matrix composites. GNP reinforcement is attributed to the homogeneous dispersion of
reinforced Cu-matrix (GNP/Cu) composites were prepared by a GNPs and grain refinement. However, the mechanical improve-
combination of the ball milling and hot-pressing processing, ment of GNP/Cu composites was still below the theoretical value.
and their mechanical properties were investigated. Microstructure The possible reasons for this deviation were discussed and
studies indicated that the GNPs with 0–8 vol.% contents were the methods for further mechanical improvement of GNP/Cu
well dispersed in the Cu matrix by ball milling. Compared to composites were proposed.

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1 Introduction Metal–matrix composites (MMCs) cost for GNP in large quantities is much lower than that for
today are extensively used in automobile and aerospace CNT. Therefore, GNP might be more suitable relative to
applications [1]. Among the promising reinforcements for CNT as an effective and economical reinforcement material
MMCs, there is a choice of different carbon allotropes and for the development of new-generation MMCs. From the
nanostructures: fullerene, carbon nanotube (CNT), nano- other side, since the discovery of graphene, there have been
fiber, and graphene. In the past decade, owing to the a considerable number of researches carried out on the
excellent mechanical and physical properties, CNT is reinforcement of a variety of polymers by GNP [9, 10].
receiving the significant attention as a novel reinforcement However, only limited researches have been done on GNP-
material for the production of advanced engineering reinforced MMCs [11–13]. This can be attributed primarily
MMCs [2]. Extensive experiments indicated that CNT can to a series of troublesome problems, including the difficulty
provide a high efficiency in properties enhancement of in homogeneous GNP distribution and full densification with
MMCs [2]. Until recently, CNT is the dominant nano-sized metal powders as well as the interfacial problems between the
carbon reinforcement for MMCs. However, the development GNP and most metallic matrices compared with polymer-
of CNT-reinforced MMCs is hindered by the complexity of based composites. Even so, early available results demon-
their dispersion in metal matrix and high cost [3]. strated that the introduction of GNPs into Al or Mg matrix
Graphene, a recently discovered two-dimensional (2D) can dramatically improve the matrix mechanical proper-
platelet consisting of carbon atoms, has attracted tremendous ties [12, 13]. To date, surprisingly no experimental studies, to
attention from the scientific communities [4]. Its unique our knowledge, have involved the preparation and charac-
mechanical and physical properties make graphene a terization of GNP-reinforced bulk Cu-matrix composites.
promising nanofiller to improve mechanical, electrical, In this study, we report the work on examining
and thermal properties of the composites [5, 6]. Recent the feasibility of fabricating bulk Cu-based composites by
experiments demonstrated an industrially viable procedure incorporation of the GNPs. Mechanical ball-milling, which
for the large-scale production of few-layered graphene has been confirmed to be very effective in the dispersion of
nanoplatelets (GNPs) [7, 8], indicating that the production CNTs in MMCs [14, 15], is also applied in attempt to

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Phys. Status Solidi A 211, No. 1 (2014) 185

uniformly disperse GNPs in Cu powders. A particular goal is the relative density of the samples. Tensile test (ASTM
to evaluate the effect of the GNP introduction on the D638) was performed using a REGER-3010 apparatus under
mechanical properties of Cu-matrix composites. a crosshead speed of 0.5 mm min1 at room temperature.
The test sample was a dog-bone shape with a gage length of
2 Experimental Cu powder (99.9% pure, 15–20 mm) 20 mm and width of 5.5 mm. Tensile stress–strain curves for
and GNPs were used to produce Cu-based composites. the reference and composite materials were obtained, and
Reagents used were of analytical grade or the highest yield strength and Young’s modulus values were measured
commercially available purity (99.9%). The exfoliated from the curves.
GNPs used in this work were obtained from natural graphite
flakes according to the modified Brodie’s method [16]. In 3 Results and discussion Figure 1 shows the
this method, graphite flakes were introduced into a solution microstructure of as-received GNPs. It is clear seen that
of H2SO4 (98%) under vigorous stirring. Then KCl was the GNPs have a relatively layered structure of platelets,
added to the mixture slowly over 30 min on the temperature demonstrating wrinkled surface texture. Nanoplatelets are
condition of 0 8C. The mixture solution was naturally stacked on top of each other, which can lead to stacks or
reached to room temperature with stirring for 96 h. After aggregates. The shape and microstructures are typical
completion of reaction, the reaction mixture was repeatedly structure of the GNPs, as reported elsewhere [5, 9, 10].
washed and filtered in distilled water to achieve an aqueous Figure 2 shows the AFM measurements of the GNPs. It is
mixture solution until the pH of the supernatant reached 7. obvious that the GNPs are well exfoliated, corresponding to
When the acidic and impurities were removed, the graphite a particle size range of 1–5 mm and a thickness around
oxide was achieved through sedimentation and finally dried 3.5 nm. The large aspect ratio of GNPs is an important factor
at 60 8C. The GNPs were finally obtained by the thermal in enhancing contact area with matrix.
reduction of graphite oxide at 1050 8C for 15 min in argon Nanofiller dispersion is an important issue since GNPs
gas atmosphere. A dispersion of GNPs in isopropyl alcohol have an inherent tendency to form agglomerates due to
((CH3)2CHOH) was conducted by sonication for 2 h to strong van der Waals attraction, large surface areas and p–p
achieve a further exfoliation. interaction [18], and therefore a good dispersion is an
In order to obtain a high dispersion of GNPs in matrix important factor for mechanical reinforcement. From the
powder, the GNPs with volume fractions of 0, 3, 5, 8, and high magnification images of the ball-milled powders shown
12% were mixed with Cu powders by ball-milling [17]. in Fig. 3, it is clear that the mixed powders with 8 vol.%
Mixed powders were each placed in a steel vial and milled by GNPs [Fig. 3(a)] give homogeneously dispersed GNPs and
a SPEX mixer in a rotary speed of 1200 rpm for 3 h under an most of GNPs are embedded into the Cu matrix powder
argon atmosphere. A ball-to-powder weight ratio of 10:1 was rather than on the surface. Nearly no GNP agglomerates
used, and petroleum ether was added as a process control can be found. This indicates that the ball-milling process
agent. As-milled powders were first compacted to a green applied in the present work is effective to achieve the
density of 75% theoretical density and then consolidated uniform mixture of the GNPs and Cu powders. Nonetheless,
using a hot pressing technique. The compact powders with increase in GNP concentration the dispersion becomes
were sintered at 800 8C for 15 min. The heating rate was more challenging, as indicated in Fig. 3(b) for 12 vol.% GNP
50 8C min1 and a pressure of 40 MPa was applied. After the powders, in which the GNP agglomerates are visible in
sintering process, the disk-shaped samples were obtained some regions.
after getting rid of the graphite felt left on the surface of the Figure 4 shows the morphology of the ball-milled
composites. powders with various GNP contents. It can be seen in Fig. 4(a)
The microstructure of the materials was characterized by
optical microscope (OM), field-emission scanning electron
microscope (FESEM) equipped with energy-dispersive
X-ray (EDX). The phase structure was identified by X-ray
diffraction spectrum taken with Cu Ka radiation at room
temperature. The size of the GNPs was identified by an
atomic force microscope (AFM). The AFM measurements
were conducted by deposition of the GNPs on a mica
substrate from an aqueous dispersion. Raman spectroscopy
was conducted to evaluate the structure change of the GNPs
using a Bruker dispersive Raman spectrometer with 532 nm
Nd: YAG laser. A maximum laser power of 3 mW was
applied on three different points of each sample for 30 s of
the accumulation time.
The density (r) of the composites was measured by
Archimedes’ principle. The theoretical densities of Cu
(8.96 g cm3) and GNP (2.2 g cm3) were used to calculate Figure 1 SEM image of as-received GNPs.

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186 K. Chu and C. Jia: Enhanced strength in bulk graphene–copper composites

Figure 2 AFM tapping-mode image (a) of GNPs and their size distribution (b).

Figure 3 SEM images of the microcosmic morphology of ball-milled (a) 8 vol.% GNP/Cu powders and (b) 12 vol.% GNP/Cu powders.

that the Cu powders become irregular in shape after ball GNPs, milled GNP-Cu mixed powders and sintered bulk
milling process, combined with increasing in particle size GNP/Cu composites. As seen, the Raman spectrum of
as well. This is due to the overwhelming ductility of Cu pristine GNPs displays clearly a G peak at 1584 cm1, a D
powders and possible dynamic recovery processes occur- peak at 1343 cm1 and a 2D peak at 2695 cm1, which are
ring, causing the Cu powders first crushed by plastic the signatures of the graphene like structure [20]. In addition,
deformation under the impact of the balls and then the Raman spectrum of pristine GNPs shows a broad 2D
subsequently cold-welded to form larger particles having peak, displaying the feature of multi-layered GNPs while the
rough surfaces [19]. However, unlike the pure Cu powders, Raman spectrum of few-layered or bi-layered GNPs shows a
GNP–Cu mixture powders show a noticeable size reduction, sharp 2D peak [20]. This is in line with AFM measurements
and this size reduction is enhanced with increasing GNP shown in Fig. 2. In contrast, the Raman spectrum of the
content, as shown in Fig. 4(b–d). This means that the GNPs in milled powders and sintered GNP/Cu composites
GNPs can play a beneficial role as grinding aids due to show no noticeable change, indicating that the intrinsic
small size and wrinkle structure of GNPs, which can structure of GNP can be well maintained in the processing.
effectively prevent the agglomeration of mixture powders. From Fig. 5, the ratios of the peak intensity between D
Such prevention of the particle agglomeration facilitates band and G band, ID/IG, are calculated, which is used
the homogeneous distribution of the GNPs within the Cu to qualitatively characterize the change of defects in the
matrix. Figure 4(e) shows the SEM image for the polished GNPs [21]. It is observed that the ID/IG ratio of milled GNPs
surface of the 8 vol.% GNP/Cu composites. The white is increased compared to that of pristine GNPs. This is
dot phases represent GNPs as determined by EDS shown mostly related to the repeated deformation, cold welding and
in Fig. 4(f). It can be found that the GNPs are still fracturing actions of the ball milling process, which can
homogeneously dispersed in Cu matrix, which suggests that cause some damage to the surfaces and edges of the GNPs.
the uniform dispersion of GNPs in ball-milled powders can Nevertheless, almost no further increased GNP defects are
be well retained in the post-sintering process. detected after sintering process.
Raman spectroscopy is a powerful nondestructive tool Figure 6 shows the XRD patterns of the GNP, Cu and
to characterize carbonaceous materials, particularly for GNP/Cu composites. For GNP, the diffraction peaks at
distinguishing ordered and disordered crystal structures of 2u ¼ 24.38 and 43.68 are attributed to the graphite-like
carbon. Figure 5 shows the Raman spectra of the pristine structure (002) and (100), respectively. For the GNP/Cu

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Phys. Status Solidi A 211, No. 1 (2014) 187

Figure 4 SEM images of the macroscopical morphology (inset shows the particle size distributions) of ball-milled (a) Cu powders;
(b) 5 vol.% GNP/Cu powders; (c) 8 vol.% GNP/Cu powders; (d) 12 vol.% GNP/Cu powders; (e) consolidated 8 vol.% GNP/Cu
composites. (f) EDS element analysis of the white dot phase marked in (e).

composites, only the peaks belonged to Cu are observed, improvement on the mechanical properties of the Cu-matrix
while no GNP peaks are detected. This can be explained by and this improvement is enhanced with increasing GNP
the small loading of GNPs in the sample and the low content. For instance, a low level of 8 vol.% GNPs added is
scattering length of carbon compared to metal atoms [22]. In found to result in a remarkable increase in yield strength
addition, the GNP/Cu composites reveal a peak broadening and Young’s modulus to 114 and 37%, respectively. The
upon milling, which suggests a reduction in matrix grain significant increase in mechanical properties of GNP/Cu
size. Furthermore, no additional peaks for the GNP/Cu composites is originally attributed to the ultra-high intrinsic
composites are identified, indicating that there is no oxides/ strength (125 GPa) and elastic modulus (1.0 TPa) of the
carbides formation in our GNP/Cu composites. GNP, which is realized by the homogeneous dispersion of
Figure 7 shows the yield strength and Young’s modulus GNPs in the Cu matrix. In addition, refining grains may
of GNP/Cu composites as a function of GNP content. It is effectively strengthen a material in terms of well-known
obvious that the addition of GNPs causes a significant Hall–Petch relation [23], which shows that the materials

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188 K. Chu and C. Jia: Enhanced strength in bulk graphene–copper composites

350 120
Pristine GNPs

Young's modulus / GPa

Milled GNP/Cu powders Yield strength 110

Yield strength / MPa

Sintered GNP/Cu composites
300 Young's Modulus
G
Intensity / (a.u.)

D 2D 100
ID /IG =0.71
250 90

ID /IG =0.69 80
200
70

ID /IG =0.52 150 60

50
0 2 4 6 8 10 12
1000 1500 2000 2500 3000
-1 GNP volume fraction / %
Raman shift / cm
Figure 7 Yield strength and Young’s modulus of GNP/Cu
Figure 5 Raman spectra of the pristine GNPs (bottom), mixed
composites versus GNP volume fraction.
powder of milled GNP/Cu powders (center), and sintered GNP/Cu
composites (top).
can be strengthened by decreasing the grain size. The grain
structure observation shown in Fig. 8 displays an average
grain size of approximately 10 mm for the Cu matrix and
4 mm for 8 vol.% GNP/Cu composites. This observation is
(111)
consistence with previous XRD analysis (Fig. 6), which
reveals a clear increase in peak width for the composites or
(200)
Intensity (a.u.)

(220) the grain refinement. Similar to CNT/metal composites [24],

GNP/Cu it is thought that the much finer grain size in GNP/Cu
(111) composites is attributed to the effective pinning effect of
the nano-sized GNPs on the grain boundaries, in which the
(200) dislocation motion could be blocked at the sites of GNPs.
(220)
Cu Consequently, the dislocation accumulation due to the
addition of GNP hinders the growth of the recrystallized
(002) grains during the processing, which contributes to the high
(100) GNP strength of GNP/Cu composites.
However, as seen in Fig. 7, with further increasing GNP
20 30 40 50 60 70 80 content up to 12 vol.%, the increments of the yield strength
ο
2θ ( ) and Young’s modulus dramatically reduce to 46 and 24%,
respectively. The less effective enhancement in 12 vol.%
Figure 6 XRD patterns of the GNP, Cu and sintered GNP/Cu GNP/Cu composites mainly arises from the GNP aggrega-
composites. tions in the ball-milled powders as shown in Fig. 3(b). The

Figure 8 Grain structures of (a) Cu-matrix and (b) 8 vol.% GNP/Cu composites.

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Phys. Status Solidi A 211, No. 1 (2014) 189

Halpin-Tsai (Randomly Ec, Eq. (1))

Young's Modulus / GPa

200 Halpin-Tsai (Undirectionally E//, Eq. (2))
100
Relative density / %

Experimental data
175
99
150
98
125
97
100
96
75
95
0 2 4 6 8 10 12 0 5 10 15

GNP volume fraction / % GNP volume fraction / %

Figure 10 Comparison between experimental data and theoretical
Figure 9 Relative density of GNP/Cu composites versus GNP calculations of Young’s moduli Ec (Eq. (1)) and E|| (Eq. (2)) for
volume fraction. GNP/Cu composites as a function of GNP volume fraction.

GNP agglomerates would form steric obstacles in compo- GNP is 1.0 TPa provided from the reported results [27].
sites consolidation, restricting matrix materials to flow into The average length and thickness of GNPs are 2 mm and
the agglomerates and resulting in the formation of pores in 3.5 nm, respectively, obtained from AFM images (Fig. 2).
the composites. This can be confirmed by the relative density Substituting these parameters into Eqs. (1) and (2), the
measurements as shown in Fig. 9, in which the relative comparison between our experiments and theoretical
density of 12 vol.% GNP/Cu composites is 96.4%, showing calculations are shown in Fig. 10. Although the incorpo-
a large amount of porosity. Subsequently, these pores act as ration of GNP can provide a marked improvement in
stress concentration sites for plastic instability, weakening mechanical performance of the composites, it is obvious that
the efficiency of the mechanical improvement by incorpo- the measurements are evidently lower than the predictions.
ration of GNPs. This implies that there is still some room for further
In order to profoundly understand the strengthening enhancement in mechanical performance of GNP/Cu
behavior of GNP/Cu composites, it is necessary to compare composites by improvement of processing and quality of
the experimental results with theoretical predictions. GNP. The gap between the predictions and experimental
The Halpin–Tsai model [25, 26] is frequently applied to results is attributed to the following reasons.
estimating the modulus of the composites in which the Reinforcement structural defects are often generated
reinforcement spatial distribution and aspect ratio are during the ball-milling process, as shown in Fig. 5, which
included. Considering the random orientation or unidirec- can result in the loss of intrinsic stiffness of the GNPs [28].
tional distribution of GNPs in the polymer matrix, the Thus the structural defects in GNP possibly reduce the
Halpin–Tsai equation is given by effective stiffness of the GNPs and further decrease the
  modulus of the composites. Aside from the issue with
3 1 þ 2=3hL pf 5 1 þ 2hT f the defects of GNPs, the reinforcing effectiveness observed
Ec ¼ Em  þ  ; ð1Þ
8 1  hL f 8 1  hT f from GNP/Cu composites may be limited by problems with
  interfacial adhesion of GNP-matrix and spatial distribution
1 þ 2=3hL pf of GNP. In general, the composite interfacial bonding can be
E jj ¼ E m ; ð2Þ
1  hL f divided into four types of mechanical bonding, physical
bonding (van der Waals interactions), diffusion bonding,
Eg =E m  1 E g =E m  1
hL ¼ ; hT ¼ ; ð3Þ and reaction bonding, with bonding strength increasing in
E g =E m þ 2=3p E g =E m þ 2 the same order [29]. In this context, the adhesion between
Cu-matrix and GNP is attributed to the type of mechanical
where E is the Young’s moduli, the subscripts g, c, || refer to bonding or van der Waals interactions due to non-wetting of
the GNP, the composites with randomly oriented and the GNP and Cu, resulting in an insufficient interfacial
unidirectionally distributed reinforcements, respectively. p bonding. Moreover, it is known that the GNP has ultra-high
and f are the aspect ratio and volume fraction of GNPs in the strength along the in-plane direction but low strength in
composites, respectively, in which p is calculated by through-thickness direction, the random distribution of
dividing the GNP length by its GNP thickness. In the GNPs with various orientations would disturb this unidirec-
calculations, the Young’s modulus of the Cu matrix is tional load transfer mechanism and reduce the strengthen
76 GPa obtained from the measurement, and that of the efficiency of the GNPs. It is shown in Fig. 10 that the

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190 K. Chu and C. Jia: Enhanced strength in bulk graphene–copper composites

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