Materials Science & Engineering A 766 (2019) 138365

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Enhanced mechanical properties and electrical conductivity of graphene T

nanoplatelets/Cu composites by in situ formation of Mo2C nanoparticles
Siyuan Guoa, Xiang Zhanga, Chunsheng Shia,c,∗, Enzuo Liua,b, Chunnian Hea,b,c, Fang Hea,
Naiqin Zhaoa,b,c
a
School of Materials Science and Engineering and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin, 300350, China
b
Collaborative Innovation Centre of Chemical Science and Engineering, Tianjin, 300072, China
c
Key Laboratory of Advanced Ceramics and Machining Technology, Ministry of Education, Tianjin University, Tianjin, 300350, China

ARTICLE INFO ABSTRACT

Keywords: Poor mechanical interfacial bonding between graphene nanoplatelets (GNPs) and Cu is unfavorable to the
Metal matrix composites comprehensive properties of the GNPs/Cu composites. Molybdenum carbide coating graphene nanoplatelets
Interface (Mo2C@GNPs) were prepared by impregnation reduction combined with in situ reaction to improve the inter-
Mechanical properties facial bonding of Cu matrix composites. Compared with GNPs/Cu composites, Mo2C@GNPs/Cu composites
Strengthening mechanism
exhibit excellent mechanical properties. It is due to the fact that Mo2C not only improves the interface bonding
Electrical conductivity
between the GNPs and Cu matrix, but also increases the strength of composites by dislocation strengthening as
nanoparticle reinforcing phase. In addition, the conductivity of Mo2C@GNPs/Cu composites is higher than that
of GNPs/Cu composites due to the improved interfacial bonding. This work sheds light on adding carbides to
control the properties of GNPs/Cu composites.

1. Introduction enhanced properties, the quality of graphene derivatives should be

Graphene, as an ideal nano reinforcing and toughening material for
composites, has a series of excellent properties such as high strength,
Young's modulus, thermal conductivity and charge carrier mobilities
[1–4]. Graphene derivatives (e.g. reduced graphene oxide (RGO) and
graphene nanoplatelets (GNPs)) are more practical than graphene be-
cause of their similar properties and easy preparation [5,6]. Graphene
derivatives reinforced Cu matrix composites have attracted a lot of
research interest in recent years, because the addition of reinforcing
phase is expected to improve the mechanical properties of Cu matrix
while maintaining its original excellent functional properties of high
electrical conductivity and thermal conductivity, which greatly expands
the application field of Cu matrix composites [7–11]. However, in order
to achieve the desired results, two main problems need to be solved: the
dispersion of graphene derivatives in the matrix and the interface
bonding between the reinforcement and Cu matrix [12,13].
Achieving the uniform dispersion of graphene derivatives in Cu
matrix is the primary problem in the preparation of Cu matrix com-
posites. Molecular mixing, electrostatic self-assembly and sheet powder
metallurgy are several common methods to reach above objectives
[14–16]. Besides, in order to obtain Cu matrix composites with
maintained while the uniform dispersion of reinforcement phase is
realized. However, the integrity of graphene structure cannot be well
preserved in most ex-situ methods. Therefore, it is a better choice to
synthesize graphene derivatives directly on the matrix powders by in-
situ synthesis, which can achieve uniform dispersion while maintaining
structural integrity [17–19].
Although the uniform dispersion of graphene derivatives in the
matrix has been greatly improved, the mechanical properties of Cu
matrix composites are far lower than the theoretical expectations, and
the potential of reinforcements have not been fully exploited [20]. This
is mainly due to the fact that the mechanical bonding cannot achieve
effective load transfer from Cu matrix to the reinforcement phase.
Therefore, reasonable interface bonding between graphene derivatives
and Cu matrix is essential for the performance of the composite mate-
rials. Because of poor wettability and reaction activity between Cu and
C, the interfacial bonding between graphene derivatives and Cu matrix
is impossible to be improved by forming carbides [21]. So many re-
searchers first thought of using metal particles to modify reinforcing
phase to improve the interfacial bonding of composites. Tang et al. [22]
modified RGO with Ni to improve the interfacial bonding with Cu
matrix, resulting in an increase in the yield strength of the composites

∗
Corresponding author. School of Materials Science and Engineering and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University,
Tianjin, 300350, China.
E-mail address: csshi@tju.edu.cn (C. Shi).

https://doi.org/10.1016/j.msea.2019.138365
Received 15 July 2019; Received in revised form 30 August 2019; Accepted 30 August 2019
Available online 31 August 2019
0921-5093/ © 2019 Elsevier B.V. All rights reserved.
S. Guo, et al.
by 94%. Subsequently, some researchers enhanced the bonding be-
tween graphite sheet and Cu matrix by electroless Ni plating, which
improved the thermal and bending properties of the composites [23].
However, due to the high cost and complex process, the practical ap-
plication is limited. Meanwhile, it has been found that the formation of
appropriate carbides at the interface between graphene derivatives and
metal matrix contributes to the improvement of interface bonding, and
the effect is more remarkable than that achieved by metal particle
coating [24]. So far, there have been some studies on improving the
interface bonding of Cu matrix composites by using carbides. For in-
stance, Si et al. [24] deposited a layer of carbide on GNPs surface by
molten salt bath, and then dispersed it uniformly in Cu matrix by mo-
lecular mixing method. Although the mechanical properties of Cu ma-
trix composites have been greatly improved, the conductivity and
thermal conductivity of composites decreased significantly compared
with pure Cu. Another common way to in-situ synthesis of carbides
between graphene derivatives and Cu is matrix alloying [25,26]. This
method improves the strength of the composites, but the carbides have
a significant negative impact on the elongation and functional proper-
ties of the composites. The effect may be partly ascribed to the dis-
continuities of material property induced by the carbides formed at the
interface between the matrix and graphene derivatives. In addition, the
inherent strengthening properties of carbides are not reflected in most
researches [24–26]. However, compared with homogeneously dis-
persed single-phase reinforced metal materials, the new generation
composite reinforced by hybrid phases with special distribution form
has greater potential to meet the requirements of engineering applica-
tions. On the other hand, there have been many studies on the
strengthening mechanism of composite materials, but most of them
focus on the effect of single reinforcement on relative strength en-
hancement [27–29], and little attention has been paid to the synergistic
mechanism of dual reinforcement phases with nanoparticles and gra-
phene derivatives.
Based on the above analysis, a new method of in-situ synthesis of
carbides and graphene derivatives is needed to be proposed, which
makes hybrid reinforcement phases have a novel distribution in com-
posites and improves the mechanical and functional properties of gra-
phene derivatives reinforced Cu matrix composites. In this work, mo-
lybdenum carbide (Mo2C) was introduced into Cu matrix composites to
improve their properties. The composite powders (Mo2C@GNPs@Cu)
were prepared by impregnation reduction and in situ reaction.
Composite bulks were prepared by subsequent hot-pressed sintering
and multi-pass hot rolling. By characterizing the structure of the com-
posites, it could be found that Mo2C was not only distributed on the
interface but also uniformly distributed near the interface (interfacial
gradient transition zone), which introduces a gradient transition of
properties from reinforcement to the matrix. Then, the strengthening
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Materials Science & Engineering A 766 (2019) 138365
Fig. 1. Schematic illustration for the fabrication
process. Raw Cu powders, Cu(NO3)2·3H2O and
H24Mo7N6O24·4H2O (a) were treated by hot-drying
and reduction to obtain Mo3O@Cu powders (b).
Followed by mixing with sucrose, hot-drying and in-
situ reaction, Mo2C@GNPs@Cu powders (c) were
prepared. Then the composite bulks were fabricated
by hot-pressing and hot-rolling (d).
mechanism of Mo2C@GNPs improving the mechanical properties of
composites and the effect of Mo2C on conductivity of GNPs/Cu com-
posites were analyzed.
2. Experimental
2.1. Materials
The atomized Cu powders (purity 99.9%, 1–3 μm, Xingye Metal
Materials Shanghai Yunyan New Material Co. Ltd., China) and cupric
nitrate trihydrate (Cu(NO3)2·3H2O, purity≥99.5%, Tianjin Kemiou
Chemical Reagent Co., Ltd., China) were used as raw materials for the
Cu matrix and nano Cu catalyst for the synthesis of GNPs. Sucrose
(C12H22O11) provided by Tianjin Kemiou Chemical Reagent Co., Ltd.,
China (purity≥99.5%) was used as solid carbon source. Ammonium
molybdate ((NH4)6Mo7O24·4H2O) was purchased from Aladdin
Shanghai Biological Technology Co., Ltd., China. All the reagents were
of analytical grade and used as received without further purification.
2.2. Fabrication of composites
As shown in Fig. 1, the fabrication process of Mo2C@GNPs/Cu
composites mainly consists of three steps.
I) Preparing process of precursor powders (MoO3@Cu) (Fig. 1a). Ty-
pically, Cu powders (20 g), Cu(NO3)2·3H2O (3.025 g) and
(NH4)6Mo7O24·4H2O (0.02 g, 0.04 g, 0.06 g, 0.08 g) were mixed in a
mixture of deionized water (30 ml) and ethanol (40 ml) under in-
tense stirring. The obtained homogeneous suspensions were va-
porized with magnetic stirring at 80 °C and dried at 70 °C in oven
for 3 h. The product was then ground to fine powders. Afterwards,
the precursors of MoO3@Cu were obtained by calcination at 400 °C
under H2 for 90 min. After the above operation, a mixed coating of
nano Cu and MoO3 was formed on the surface of Cu powders.
II) In-situ reaction process (Fig. 1b and c). The precursor powders and
sucrose (0.2 g, 0.3 g) were added in a mixture of distilled water
(20 ml) and alcohol (40 ml). Then, the suspensions were stirred and
evaporated at 75 °C followed by drying at 70 °C in vacuum oven.
The Mo2C@GNPs@Cu composite powders were prepared through
in-situ reaction by calcining the powders for 10 min with H2 as
reducing gas and Ar as protecting atmosphere at 800 °C, during
which the MoO3 in the coating and on the surface of the coating
was converted to Mo2C.
III) Forming process (Fig. 1d). The composite powders were loaded in
graphite die with an internal diameter of 30 mm. Vacuum hot
pressing sintering system was used to consolidate the mixed pow-
ders. The vacuum, applied pressure, sintering temperature and
S. Guo, et al.
sintering time were adjusted to below 10−4 MPa, 50 MPa, 850 °C
and 1 h, respectively. Then, the hot-pressed bulks were further
densified by multi-step hot rolling. The rolling temperature,
holding time, and single pass reduction were 800 °C, 2 min and
0.1–0.2 mm. The final accumulative reduction of the samples was
50%.
For comparison, pure Cu sample and GNPs/Cu composites were also
prepared using the same process. The precursor powder, composite
powder and composite bulk samples are denoted as symbols PP, CP and
CB, respectively. The volume fractions of GNPs and Mo2C in the sam-
ples are marked after the symbols to distinguish them. For instance, the
composite powders of Cu: Cu(NO3)2·3H2O: H24Mo7N6O24·4H2O: su-
crose = 20: 3.025: 0.04: 0.2, containing 1.6 vol% GNPs and 0.11 vol%
Mo2C, are labelled as CP-1.6–0.11.
2.3. Characterization
The field emission scanning electron microscope (SEM, Hitachi
S4800) and energy-dispersive X-ray spectroscopy (EDS) were used to
characterize the morphologies of raw powders, composite powders and
fracture surfaces of tensile samples. Transmission electron microscope
(TEM) and scanning TEM (STEM) observations were conducted on
JEOL JEM-2100F equipped with an EDS detector to reveal the interface
of the composite bulks. X-ray diffraction (XRD) patterns were obtained
with a Rigaku D/max diffractometer with Cu Kα radiation at a wave-
length of 0.15406 nm to determine the phase component of composite
powders. Raman spectroscopy (Renishaw inVia Raman microscope)
with a 532 nm Ar+ laser was used to validate the existence of GNPs and
characterize the quality of GNPs. X-ray photoelectron spectroscopy
(XPS) analysis of composite powders were performed on a PHI 1600
ESCA system using 300 W Al Ka radiation. Electron backscattered dif-
fraction (EBSD) analysis was performed by using an HKL Channel 5
system to evaluate the average grain size of the composites.
Hardness tests (Vickers hardness) of composites were conducted on
an Everone MH-6 test machine with a load of 200 g and dwelling time
of 10 s. Each sample was tested 10 times and standard deviation was
calculated. The tensile tests according to the metal materials test
standard of ASTM E8M-04 [30], were carried out on a universal ma-
terial testing machine (Lloyd (AMETEK) EZ 20) with a crosshead speed
of 0.5 mm min−1. The dog-bone shape tensile specimens with a gauge
length of 12 mm, a gauge width of 3 mm and a thickness of 1.2 mm
were machined by linear cutting machine and five tensile tests were
performed for each sample. The electrical conductivities of the com-
posite bulks (12 mm × 12 mm × 1.2 mm) were measured with an eddy-
current instrument.
3. Results
3.1. Microstructural characterization
The SEM morphologies of raw powders and the EDS of the com-
posite powders are shown in Fig. 2 and Fig. S1. As can be seen, the
original spherical Cu powders (Fig. 2a) with the size distributions of
1–3 μm have fairly smooth surface. After impregnation and reduction,
obvious coatings are observed on the surface of Cu powders (Fig. 2b, d).
Comparing PP-1.6–0.11 with PP, there are more prominent small pro-
tuberances distributed uniformly on the surface of the mixed coatings
containing MoO3 and nano Cu. It shows that the addition of
(NH4)6Mo7O24·4H2O has a significant effect on the morphology of the
coatings. After in-situ reaction, translucent folded lamellar structures
are observed and there is no obvious agglomeration, indicating that
GNPs are uniform formed on the surfaces of these powders (Fig. 2c, e, f;
Figs. S1a–d). The presence of Mo on the surface can be confirmed by
EDS analysis (Fig. 2g). From the above results, it can be concluded that
Mo can be added into the composite powders by this method, and the
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Materials Science & Engineering A 766 (2019) 138365
addition of Mo has no obvious effect on the formation of GNPs.
In order to further determine the type of molybdenum compounds
in the composite powders and the quality of GNPs, XRD and Raman
spectroscopy were used to characterize the composite powders. The
XRD pattern shown in Fig. 3a presents three diffraction peaks at 43.0°,
50.4° and 74.1°, which correspond to (111), (200) and (220) reflections
of Cu, respectively [31]. No characteristic peaks of GNPs are found. The
characteristic peak of Mo2C appears at 39° in CP-1.6-0.11 but the
characteristic peaks of MoO3 are not detected, which indicates that Mo
mainly existed in Mo2C in the composite powders [32]. As shown in
Raman spectra in Fig. 3b and Fig. S2a, obvious D band (1350 cm−1), G
band (1580 cm−1) and 2D band (2700 cm−1) can be observed. The
widening of 2D band is mainly due to the influence of the number of
layers of GNPs and the curvature of GNPs [33]. The ratio of intensity of
D/G band (ID/IG) is generally used to evaluate the structural defects in
graphene materials [34]. Compared with CP-1.6, the ID/IG value of CP-
1.6-0.11 changes from 0.67 to 0.94, indicating that the defects of GNPs
are increased. It may be due to the reaction between Mo and C, which
destroys the structure of GNPs and implies the formation of Mo2C. The
elemental composition of CP-1.6–0.11 was analyzed by XPS char-
acterization. The total spectrum (Fig. 3c) shows that the sample con-
tains four elements: Cu, O, C and Mo. Mo3d spectrum (Fig. 3d) can be
further divided into four characteristic peaks. The two peaks at
228.4 eV and 231.7 eV can be assigned to Mo3d5/2 and Mo3d3/2 of
Mo2+, which is from Mo2C. Other two peaks at binding energies of
232.3 eV and 235.7 eV, corresponding to Mo6+3d5/2 and Mo6+3d3/2,
respectively, consistent with the XPS data for pure Mo2C [35]. The C1s
spectrum (Fig. S2b) further shows an asymmetric tail towards higher
binding energy. The main peak of 284.8 eV indicates that most carbon
atoms exist as of graphite carbon (sp2 carbon) and are arranged in
conjugated honeycomb lattices. The peaks at 286.5 eV, 288.8 eV and
284.6 eV represent C–O bond, C]O bond and Mo2C, respectively [36].
After Cu matrix in the composite powders was corroded by FeCl3 so-
lution acidized with hydrochloric acid, the morphology of GNPs and the
distribution of Mo2C were characterized by TEM and EDS. As shown in
Fig. 3e and Fig. S3, GNPs show obvious layered structure and no ag-
glomeration of Mo2C is observed, which indicates that in situ reaction
not only realizes the preparation of GNPs and Mo2C, but also ensures
the uniform dispersion of Mo2C.
The morphology of the sintered and hot-rolled composite bulks is
shown in Fig. 4 and Fig. S4. From the SEM images, it can be seen that
there are residual corrosion products on the surface of each group of
composite bulks. Compared Fig. 4a (Figs. S4a and b) with Fig. 4b (Figs.
S4c and d), translucent GNPs are observed on the surface of the com-
posite bulks. Besides, the presence of Mo2C has no significant effect on
the distribution of GNPs. The above characterization results show that
GNPs can maintain structural integrity and homogeneous dispersion in
hot rolling process, which is of great significance to regulate the
properties of composite bulks. SEM image (Fig. 4c) and corresponding
EDS mappings of CB-1.6-0.11 show the uniform distribution of Mo and
C elements in the composite bulks, which proves that GNPs and Mo2C
are uniformly dispersed in Cu matrix.
A typical TEM image of CB-1.6 is displayed in Fig. 5a. It can be
observed that GNPs are tightly embedded in the Cu matrix after hot
pressing and rolling. GNPs distribute on the grain boundary of Cu
matrix, which effectively hinders grain growth. Higher magnification
observations (Fig. 5b–d) show that the interface between the Cu matrix
and the GNPs has a clear transition zone, and no voids and impurities,
indicating a good interface bonding. This is mainly due to the in situ
reaction. On the other hand, because there is no interfacial reactant at
the interface between Cu matrix and GNPs, the wettability is poor [37].
The interfacial bonding mainly depends on mechanical bonding (weak
interface bonding), which may be detrimental to the properties of the
composites [38].
Fig. 6 Displays TEM images around the interfaces between the MoC2
coated GNPs and Cu matrix in CB-1.6–0.11. The GNPs region with
S. Guo, et al. Materials Science & Engineering A 766 (2019) 138365

Fig. 2. Morphologies of raw powders, precursor powders and composite powders: (a) raw Cu powders; (b) PP; (c) CP-1.6; (d) PP-1.6–0.11; (e), (f) CP-1.6–0.11; (g)
EDS of CP-1.6–0.11.

Fig. 3. (a) XRD patterns and (b) Raman spectra of CP-1.6 and CP-1.6–0.11. (c) XPS survey spectrum and corresponding (d) high-resolution Mo3d spectra of CP-
1.6–0.11. (e) TEM image of Mo2C@GNPs.

white brightness can be clearly seen in Fig. 6a, e. Similar to that in CB-
1.6 samples, GNPs are distributed on the grain boundaries of Cu matrix
and the content of GNPs is the same, which indicates that there is si-
milar grain refine effect in the two composites. Besides, the HRTEM
image in Fig. 6b shows that there are granular substances between the
GNPs and Cu matrix. To further determine the phase of particles, fast
Fourier transform (FFT) is applied to Area 1 in Fig. 6b, the (121), (002)
and (121 ) diffraction spots of Mo2C are exhibited in Fig. 6c, which
indicates the distribution of Mo2C at the interface between the GNPs
and Cu matrix. Due to the existence of Mo2C at the interface of com-
posites, its influence on the interfacial bonding between the GNPs and
Cu matrix needs to be explored. Firstly, the formation of Mo2C requires
the participation of C element, and GNPs defects increase with the
formation of Mo2C as shown in Fig. 3b and Fig. S2a. All these features
demonstrate that there is a good bonding between Mo2C and GNPs at
the interface. Afterwards, in order to illustrate the interface bonding
between Cu matrix and Mo2C, FFT is applied to Cu matrix. Through
superimposing Fig. 6c and d, the crystallographic relation between Cu

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S. Guo, et al. Materials Science & Engineering A 766 (2019) 138365

Fig. 4. SEM images of (a) CB-1.6; (b) CB-1.6–0.11; (c) EDS mappings of CB-1.6–0.11.

matrix and the Mo2C can be obtained. The inset of Fig. 6b shows the
orientation relationship of Mo2C–Cu: (121)Mo2C//(111)Cu and
[21 0]Mo2C//[011 ]Cu. Based on the interplanar spacings of (121)Mo2C
and (111)Cu (Fig. 6b), the semi-coherent interface is formed by
matching ten (121)Mo2C planes with eleven (111)Cu planes. Compared
with the incoherent interface formed between the GNPs and Cu matrix,
the semi-coherent interface has lower interface energy, so the interface
bonding between the GNPs and Cu matrix is improved [25]. In con-
clusion, Mo2C has good interfacial bonding with both the GNPs and Cu
matrix, which can effectively improve the interfacial bonding of com-
posites and regulate the properties of composites.
In order to further characterize the distribution of Mo2C in the
composites, more detailed TEM and HRTEM characterizations of CB-
1.6–0.11 were carried out. It can be seen from TEM images (Fig. 7a, d)
that Mo2C is uniformly dispersed on GNPs without obvious agglom-
eration. It is verified from another aspect that the process of impreg-
nation and reduction realized the uniform dispersion of
Fig. 5. (a), (b) TEM images of CB-1.6; (c), (d) HRTEM images of CB-1.6.
(NH4)6Mo7O24·4H2O and the synthesis of GNPs and Mo2C simulta-
neously occurred during in situ reaction. The HRTEM images near the
interface are shown in Fig. 7b, c, e, f. More Mo2C particles are observed

Fig. 6. (a) TEM image of CB-1.6–0.11; (b) HRTEM image of the white square zone in (a); (c) and (d) FFT of Area 1 and Area 2 in (b), the inset of (b) is the
superposition of (c) and (d); (e) TEM images of CB-1.6–0.11 taken with the incident beam parallel to the Cu [011 ], (f) HRTEM images of (e).

5
S. Guo, et al.
Fig. 7. (a), (d) TEM images of CB-1.6–0.11; (b), (c), (e), (f) HRTEM images of CB-1.6–0.11; (g) STEM image and EDS mappings of CB-1.6–0.11.
at the interfaces between the GNPs and Cu matrix. It is also verified that
Mo2C not only exists at the interface between the GNPs and Cu matrix,
but also distributes evenly in Cu matrix adjacent to GNPs. A locally
uniform distribution of Mo2C around GNPs is formed. The chemical
composition of CB-1.6–0.11 is analyzed by STEM elemental mapping
and the resulting elemental distribution maps for Cu, C and Mo are
presented in Fig. 7g and Fig. S5. It can be clearly seen that Mo element
exists not only in the distribution area of C element, but also at the
interface of Cu element and C element, and in a small area around the
interface. This results in an interfacial gradient transition zone between
GNPs and Cu matrix, which will further improve the mechanical
properties of composites. This is similar to the distribution of Mo2C
observed in Fig. 7a–f, which further verifies the distribution area of
Mo2C in the composite materials. The above characterization results
show that Mo2C not only plays a role in modifying the interface of the
composites, but also can be considered as a reinforcing phase dis-
tributed around GNPs.
3.2. Mechanical properties
Fig. 8a and b demonstrates the tensile properties of pure Cu and the
composites. The key mechanical properties of yield strength (YS), ul-
timate tensile strength (UTS) and elongation (E) are also listed in Table
S1. The addition of GNPs and Mo2C causes a marked strength en-
hancement of the composites. The YS and UTS of CB-1.6 reach to
~246 MPa and ~275 MPa, which are 40% and 18% higher than those
of CB, respectively. Although the mechanical properties of CB-1.6 have
been improved remarkably, they are far from the theoretical value.
Notably, CB-1.6–0.11 exhibits the further improved YS of 303 MPa and
UTS of 330 MPa, 23% and 20% higher than those of CB-1.6. Then,
through comparing the mechanical properties of the composites in
Fig. 8b, it is found that the mechanical properties of the composites
decrease with the increase of GNPs content, which may be due to the
unavoidable agglomeration of the high content of GNPs. Moreover, the
tensile properties of composites first increased and then decreased with
increasing Mo2C concentration. Furthermore, the hardness of the
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Materials Science & Engineering A 766 (2019) 138365
composites was tested, and the results are shown in Fig. 8c. The change
trend of hardness of composites with reinforcing phase is increasing
first and then decreasing, while CB-1.6-0.11 shows the optimal per-
formance, which increased by 40% and 14% respectively compared
with CB and CB-1.6. It is noteworthy that the strength and hardness of
Cu matrix composites reinforced with Mo2C@GNPs are generally better
than that reinforced with GNPs. This is mainly due to the fact that the
Mo2C not only forms interfacial transition zone between the GNPs and
Cu matrix, but also acts as a particle reinforcement phase. However, the
structural integrity of GNPs decreases gradually with the increase of
Mo2C content, which will reduce the intrinsic strength of GNPs. The
above results show that the addition of Mo2C is beneficial to the im-
provement of mechanical properties of GNPs/Cu matrix composites, but
an optimal content of Mo2C exists.
3.3. Electrical conductivity
The evolution in the electrical conductivity with respect to the Mo2C
content is shown in Fig. 8d. Compared with GNPs reinforced Cu matrix
composites (CB-1.6 and CB-2.5), when adding 0.055 vol% Mo2C, the
conductivity of Cu matrix composites are increased by 3.5% IACS (CB-
1.6–0.055) and 6.0% IACS (CB-2.5–0.055), respectively, but then de-
crease with the increase of Mo2C content. The lower conductivity of the
Cu matrix composites only containing GNPs might be due to the poor
interface bonding between the GNPs and Cu matrix, resulting in the
formation of scattering centers at the interface. Adding a small amount
of Mo2C, the interfacial bonding of the composites is improved, and the
conductivity of the composites is increased significantly. As the con-
ductivity of Mo2C is poor and the structure of GNPs is destroyed by the
formation of Mo2C, the increase of Mo2C content has a negative effect
on the conductivity of the composites. Even so, the conductivity of the
composites containing Mo2C up to 0.22 vol% remains above 90% IACS,
which is generally higher than that of the samples only using GNPs as
the reinforcing phase. The above results show that due to the low
content of Mo2C, the effect of interface control on the conductivity of
Cu matrix composites is dominant.
S. Guo, et al. Materials Science & Engineering A 766 (2019) 138365

Fig. 8. (a) Engineering stress-strain curves of pure Cu and composite bulks with 1.6 vol% GNPs; (b) Strength and fractural elongation comparisons of pure Cu and
composites; (c) Hardness of pure Cu and composite bulks; (d) Electrical conductivity of composite bulks.

4. Discussion have good elongation. In the magnified fracture images of composite

4.1. Distribution of hybrid reinforcing phases and fracture mechanism of the
composites
Based on the characterization results of the composites, the sche-
matic diagrams of distribution of the reinforcement phase in Cu matrix
composites with GNPs as a single reinforcement phase and Cu hybrid
composites are shown in Fig. 9a and b. For the composites with single
reinforcement phase, the GNPs are homogenously distributed in Cu
matrix parallel to the rolling direction after repeated rolling. However,
the hybrid reinforcement phase presents a special distribution. On the
whole, the hybrid reinforcement phase is uniformly distributed in the
matrix by in-situ reaction, but locally, Mo2C is distributed on the in-
terfaces between GNPs and Cu matrix and in approximately 30 nm
range around the GNPs in the hybrid reinforcement phase.
To further clarify the reinforcing mechanism of the composites, the
fracture behavior of the composites was analyzed. In the several groups
of samples shown in Fig. 10a, c, e and Figs. S6a and c, the existence of
obvious deep dimples can be observed, indicating that the addition of
the reinforcing phase has no obvious influence on the ductile fracture of
Cu matrix, which is also consistent with the fact that the composites
materials, it can be observed that there are obvious translucent flake
GNPs in the dimples (marked by white arrow in Fig. 10d, f), which is in
sharp contrast with the clean dimple of the pure Cu, indicating that
GNPs has a significant influence on the fracture process of the com-
posite materials. By comparing Fig. 10d (Fig. S6b) with Fig. 10f (Fig.
S6d), obvious GNPs pull-out and peel-off layers can be observed at the
fracture surface of the sample containing only GNPs, while GNPs is
tightly embedded in the matrix in the sample with Mo2C@GNPs as the
reinforcement phase, indicating that GNPs break up during the fracture
process. The presence of Mo2C in the fracture surface can be obtained
from the EDS images of CB-1.6–0.11 (Fig. S6e), which indicates that the
fracture of GNPs is related to interface improvement caused by the
addition of Mo2C.
According to the fracture behavior, the schematic diagrams of the
two different fracture behaviors of the composites are shown in Fig. 10g
and h. In GNPs reinforced Cu matrix composites, the pull-out of GNPs at
the fracture surface indicates that the mechanical bonding between Cu
and GNPs [39]. While the fracture of GNPs, which indicates that the
hybrid reinforcement phases (Mo2C@GNPs) with semi-coherent re-
lationship with Cu matrix have better interface bonding than the single
reinforcement phase (GNPs). It shows that Mo2C at/near the interface

Fig. 9. Schematic diagrams of hybrid reinforcing phases distribution of (a) GNPs, (b) GNPs@Mo2C.

7
S. Guo, et al.
Fig. 10. SEM images of the fracture surfaces of (a), (b) CB; (c), (d) CB-1.6; (e), (f) CB-1.6–0.11, and schematic diagrams of fracture mechanisms (g) GNPs, (h) GNPs@
Mo2C.
hinders the pull-out of GNPs and facilitates the load transfer from Cu
matrix to the GNPs, and improves the strength of the composites.
Meanwhile, it also indicates that GNPs with excellent interface transi-
tion plays a role in bridging cracks during fracture, which will greatly
consume fracture energy. Even when the GNPs finally breaks, elastic
vibration will increase energy consumption and improve the toughness
of composites.
4.2. Strengthening mechanisms
In the composites with discontinuous reinforcing phases, the en-
hancement of strength is closely related to the morphology, distribu-
tion, volume fraction of reinforcing phases, the interface bonding be-
tween reinforcing phases and the matrix, and the effect of reinforcing
phases on the matrix. Considering these factors, the improvement of
strength of the composites is mainly classified in the following three
aspects: (i) the change of strength of Cu matrix; (ii) the strengthening
effects of Mo2C particles; (iii) the strengthening mechanism of GNPs.
As the basis of strength improvement of composites, the effects of
reinforcement phases on Cu matrix are considered first. According to
the existing research, even if a small amount of reinforcement phase is
added into the metal matrix, it will produce obvious grain refinement
effect. The grain size distributions in CB and CB-1.6–0.22 were in-
vestigated through EBSD analysis (Fig. 11). The results show that the
average grain size of CB is 5.88 μm. CB-1.6-0.11 has more uniform grain
distribution, and the average grain size is reduced to 1.12 μm. The grain
refining effect is mainly attributed to the fact that the reinforcing phase
hinders the growth of the grains in the Cu matrix during the forming
process. For the grain sizes in microns, the improvement of YS by grain
refinement ( GR ) can be calculated by Hall-Petch relationship [40] as
following:
8
Materials Science & Engineering A 766 (2019) 138365
GR = K (dc 0.5 d m0.5) (1)
where K is a constant (0.07 MPa m0.5 for Cu), dc and dm are the average
grain sizes for the composite and pure Cu, respectively. The value of
GR is calculated to be 37.3 MPa. Therefore, the YS of Cu matrix
( m = o + GR ) in composites is 213.3 MPa.
Due to the proper morphology and overall uniform distribution of
particle reinforcing phase (Fig. 3e), the strength effect can be mainly
attributed to two aspects. On the one hand, the particle reinforcing
phase can also bear stress through load transfer mechanism. On the
other hand, the introduction of particles with high hardness into Cu
matrix will lead to the accumulation of dislocations around the parti-
cles, resulting in dislocation strengthening. By considering the sy-
nergistic effect, Ramakrishnan combined a modified shear-lag model
with an enhanced dislocation density model to obtain a compound
analysis model [41]. According to this model, the strengthening effect
of Mo2C particles ( Mo2C ) can be expressed by the following formula:
Mo2C = m [(1 + fl )(1 + fd ) 1] (2)
where fl and fd are strengthening factors related to load-bearing and
dislocation density, respectively.
In the above formulas, the increase of YS due to load-bearing ( l )
can be expressed as:
= 0.5VMo2 C (3)
l m
where VMo2C represents the particle volume fraction (0.11 vol%).
Therefore, it can be deduced that fl = 0.5VMo2C. The general expression
for fd is
fd = d
m (4)
S. Guo, et al. Materials Science & Engineering A 766 (2019) 138365

Fig. 11. EBSD results of (a) CB; (b) CB-1.6–0.11.

where d is the increase in the yield strength caused by dislocation important for Orowan strengthening [45]. Therefore, the contribution
strengthening as [41,42]: of Orowan mechanism to the strength of composite materials can be
neglected due to the quasi-two-dimensional structure and large aspect
d = ( Orowan )
2 +( CTE )
2 +( EM)
2
(5) ratio of the in-situ synthesized GNPs [46]. In addition, the thermal
where Orowan is the increase in the YS of composites due to the Or-
mismatch strengthening is not well applied here, mainly because GNPs
owan mechanism, CTE is caused by different coefficient of thermal
has a flexible structure [12]. Based on the above analysis and the
expansion between Mo2C particles and Cu matrix, EM is the strength fracture behavior of the composites, the enhancement effect of GNPs is
improvement by the modulus mismatch. mainly attributed to the load transfer mechanism. Load transfer is
The Orowan stress ( Orowan ) can be estimated by [43]: closely related to the shear-lag of GNPs with strong interfacial bonding
under tensile load, so its contribution to the yield strength of compo-
0.13Gm b d Mo2 C sites can be expressed by the shear-lag model as [47]:
= ln
Orowan
2b (6)
S
where Gm is the shear modulus (42.1 GPa for Cu), b is the Burgers = VGNPs ( )( m )
GNPs
A 4 (9)
vector (0.256 nm for Cu), d Mo2 C is the average diameter of Mo2C par-
ticles (~10 nm), is the interparticle spacing, expressed as: where VGNPs is volume fraction of GNPs (1.6 vol%), S is the interfacial
area, and A is the cross-sectional area (S = 2(w + t ) lG NPs , A = wt ; w, t
1 1
= d Mo2 C [( )3 1] and lGNPs are the width (~50 nm), the thickness (~6 nm) and the length
2VMo2C (7) (~150 nm) of GNPs, respectively). Meanwhile, Mo2C is distributed
the value of the Orowan stress obtained here is the upper limit value. around the GNPs (interfacial gradient transition zone, within 30 nm),
Because Mo2C is not only distributed in the grain interior, but also at which will affect the strength of Cu matrix around GNPs. Therefore, the
the grain boundary. Therefore, the volume fraction of Mo2C matching surrounding distribution term ( s d ) can be introduced into Eq. (9) to
the Orowan mechanism can be approximately expressed as modified the matrix strength term ( m = m + s d ). According to the
VMo2 C t = 0.5VMo2C . size of GNPs and the distribution range of Mo2C, the content of Mo2C
According to the relevant literature, only the samples which have around GNPs is 0.6 vol% by simple mathematical calculation. The value
undergone rapid cooling after sintering can produce obvious thermal of s d can be calculated by Eq. (2). According to the above for-
mismatch effect. Furthermore, for nanoparticles less than 50 nm in size, mulas, the strengthening effect of load transfer mechanism is 68.4 MPa.
the strain mismatch between the reinforcement phase and Cu matrix In this research, there are two reinforcing phases (GNPs and Mo2C)
caused by thermal mismatch cannot form dislocations [43]. Therefore, in the composites. The effect of the synergistic reinforcing effect on the
the CTE term of Mo2C can be ignored. YS of the composites can be expressed as [42]:
Finally, the stress increasement due to modulus mismatch ( EM ) is 1
[41,44]: Mo2 C@GNPs = ( q
Mo2C + q
GNPs)q
(10)

VMo2C b where the value of q is between 1 and 2. Considering the effect of Cu

EM = Gm matrix and the reinforcing phase, the yield strength of Cu matrix
d Mo2 C (8)
composites can be expressed as follows:
where is the material-specific coefficient (~0.4), is the strain of the
c = o + GR + Mo2 C@GNPs (11)
composite (0.2%).
Generally, load transfer, Orowan and thermal mismatch mechan- When q = 1.6, the theoretical and experimental values of the
isms are used to describe the strengthening effect of GNPs. It should be composites are approximately equal ( c =303.8 MPa), which indicates
pointed out here that the aspect ratio of the reinforcing phase is very that the yield strength of composites has been successfully modeled.

Fig. 12. Contribution ratios of different strengthening mechanisms.

9
S. Guo, et al.
The specific calculation values of each term are shown in Table S2 and
the contribution ratios of different strengthening mechanisms are
shown in Fig. 12.
Through the above analysis, although only a small amount of re-
inforcement phases is added, Cu matrix has obvious grain refining ef-
fect. The strengthening effect of GNPs mainly comes from the load
transfer mechanism. In contrast, the strengthening effect of Mo2C is
mainly dislocation strengthening, and the effect of load transfer is not
obvious. It is noteworthy that strength improvement of Cu matrix
around GNPs caused by the distribution form of hybrid reinforcing
phases also plays an important role in improving the YS of composites.
5. Conclusions
In summary, Mo2C@GNPs reinforced Cu matrix composites were
successfully prepared by impregnation reduction, in-situ reaction and
subsequent forming processes. A new distribution form of hybrid re-
inforcing phases with uniform distribution of Mo2C at/near the inter-
face between the GNPs and Cu matrix was obtained. As a result, the
0.11 vol% Mo2C@1.6 vol% GNPs/Cu composites had good mechanical
properties. The YS of the composites reached 303 MPa, which were
72% and 23% higher than that of pure Cu and the 1.6 vol% GNPs/Cu
composites, respectively. Through the analysis of the corresponding
strengthening mechanism of GNPs and Mo2C and the fracture behavior
of the composites, it is found that the new distribution of Mo2C in
composites not only improved the interface bonding between the GNPs
and Cu matrix, but also played a role of nanoparticle reinforcement. In
addition, the local distribution of the particle reinforcing phases sur-
rounding GNPs also has an obvious effect on the load transfer of GNPs
compared with the uniform distribution. The electrical conductivity of
the composites reinforced with Mo2C@GNPs is above 90% IACS be-
cause the interface improvement effect of Mo2C is dominant. This study
regulates the properties of GNPs/Cu matrix composites by using car-
bides with interfacial improvement, and provides a new idea for the
subsequent design of reinforcing phase distribution.
Disclosure statement
No potential conflict of interest was reported by the authors.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
Acknowledgements
The authors acknowledge the financial support from the National
Natural Science Foundation of China (No. 51571147).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.msea.2019.138365.
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