Composite Interfaces

ISSN: 0927-6440 (Print) 1568-5543 (Online) Journal homepage: https://www.tandfonline.com/loi/tcoi20

Microstructure and properties of graphite/copper

composites fabricated with Cu-Ni double-layer
coated graphite powders

Yue Yuan, Xueping Gan, Yuanteng Lai, Qi Zhao & Kechao Zhou

To cite this article: Yue Yuan, Xueping Gan, Yuanteng Lai, Qi Zhao & Kechao Zhou (2019):
Microstructure and properties of graphite/copper composites fabricated with Cu-Ni double-layer
coated graphite powders, Composite Interfaces, DOI: 10.1080/09276440.2019.1644051

To link to this article: https://doi.org/10.1080/09276440.2019.1644051

Published online: 19 Jul 2019.

Submit your article to this journal

Article views: 1

View Crossmark data

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=tcoi20
COMPOSITE INTERFACES
https://doi.org/10.1080/09276440.2019.1644051

Microstructure and properties of graphite/copper composites

fabricated with Cu-Ni double-layer coated graphite powders
Yue Yuan, Xueping Gan, Yuanteng Lai, Qi Zhao and Kechao Zhou
State Key Laboratory of Powder Metallurgy, Central South University, Changsha, China

ABSTRACT ARTICLE HISTORY

In this paper, graphite/copper composites with high perfor- Received 4 April 2019
mance were fabricated by a novel two-steps electroless plating Accepted 12 July 2019
and spark plasma sintering. The interfacial characterization and KEYWORDS
modification mechanism of nickel coating in the composites Graphite/copper composites;
were analyzed. Effects of sintering temperature and Ni volume electroless plating; spark
fraction on the mechanical properties and microstructure of plasma sintering; interface;
composites were also systematically investigated. The results microstructure; mechanical
showed that the introduction of Ni coating could significantly properties
improve the interfacial bonding between Cu matrix and
graphite and led to the uniform distribution of graphite parti-
cles in Cu matrix. Moreover, the mechanical properties of com-
posites increased obviously with the increase of Ni coating
content from 0 vol.% to 10 vol.%. When the Ni content was
10 vol. %, the relative density, hardness, and compressive
strength of the composites reached to 99.8%, 67.8 HB and 314
MPa, respectively.

CONTACT Xueping Gan ganxueping@csu.edu.cn State Key Laboratory of Powder Metallurgy, Central South
University, Changsha 410083, China
© 2019 Informa UK Limited, trading as Taylor & Francis Group
2 Y. YUAN ET AL.

1. Introduction
Graphite/copper composites are used as heat sinks, brushes, contact strips for pantographs
and sealing rings due to their excellent electrical and thermal conductivity, solid lubricating
and low thermal expansion coefficient [1–3]. With rapid development of aerospace industry,
the requirements of high performances are put forward for sealing ring materials made of
graphite/copper composites. These materials should possess properties of hardness >38 HB,
compressive strength >160 MPa and relative density >99% [4]. However, graphite cannot be
wetted by copper which hinders the bonding between the graphite and Cu matrix, and
shortens the service life of the composites [5]. Meanwhile, significantly different densities
between graphite particles (2.27 g/cm3) and copper powders (8.96 g/cm3) give rise to the
difficulty to prepare dense composites with homogeneously distributed graphite particles
through infiltration and conventional powder metallurgy method. Therefore, two major
issues should be solved to improve the performance of graphite/copper composites: weak
interface bonding between two phases, and uneven distribution of graphite particles in copper
matrix.
An effective approach to improve interfacial bonding is a surface treatment of
graphite particles by preparing metallic coating, such as plasma deposition, physical
vapor deposition, electroplating and electroless plating [3,6,7]. Among these methods,
electroless plating has been widely used in surface coating technology because of its
advantages of flexibility, simplicity, uniformity and low-cost [8–10]. Recently, many
researches indicated that the interfacial bonding between graphite and metal matrix
could be effectively improved by plating Ni [11–14] and Ni-based alloys [15,16] on
graphite particles. Two mechanisms were discussed in such method. On one hand,
nickel has good wettability with graphite [17,18]. On the other hand, Ni plating
facilitates the formation of solid solution (such as Cu-Ni solid solution [19,20], Al-Ni
solid solution [13]) or intermediate compound with metal matrix (such as Al3Ni, Al3Ni2
[13,21]) at graphite–metal interface, which can effectively reduce the interface energy
and improve the interfacial bonding between the graphite and metal matrix. Therefore,
the composites with nickel coating exhibited better tribological performance and
mechanical performance than those without nickel coating. Therefore, Ni-coated layer
was used to improve the interfacial wettability by electroless plating in this study.
Although surface-modified graphite can significantly improve the interfacial bonding
between copper matrix and graphite, the relative density of graphite/copper composites
(less than 99%) and the uniformity of graphite distribution in composites are still not
satisfactory in most reports [3,6,15,16,22]. Because these composites were usually made by
conventional powder metallurgy method: mixing copper powders and graphite particles
and then compacting and sintering. However, the two phases cannot be homogeneously
mixed on account of different densities. Meanwhile, the metallic coating on graphite can be
easily destroyed during the mixing process, which would seriously affect the strength,
density, friction and wear properties of the composites. Therefore, copper was deposited
onto the graphite by electroless plating in this study. The copper layer was thick enough to
replace copper powders as the matrix. In this way, the powder mixing step was eliminated,
and graphite particles were no longer unevenly distributed in Cu matrix [23].
Currently, spark plasma sintering (SPS) has attracted considerable attention for the devel-
opment of high-performance metal matrix composites (MMCs) and alloys [22,24–27].
 COMPOSITE INTERFACES 3

Compared with conventional sintering processes, SPS is carried out at lower temperature and
costs less time due to the application of pulse current for heating the powders. In addition,
during a current pulse, the instantaneous spark discharge between powder particles can
generate high-temperature plasma, which can effectively remove adsorbed gases and oxides
from the surface of the powders and contribute to the formation of active contact between
them [22]. Therefore, the application of SPS to fabricate graphite/copper composites is very
promising to attain desirable relative density and mechanical properties.
In this study, graphite was coated with nickel to improve the bonding at the inter-
face. Then, the Ni-coated graphite was deposited with copper to replace copper powder
addition. The obtained Cu-Ni double-layer coated particles were directly compressed
and sintered in SPS system. As such, the copper layer can effectively prevent uneven
distribution of copper powders during mixing, and graphite/copper composites with
strong interfacial bonding and homogeneously distributed graphite particles were
obtained. The interface characterizations and modification mechanism of nickel coating
were studied. The effects of the sintering temperature, the Ni-P volume fraction on the
mechanical properties and microstructure of composites were also investigated.

2. Experimental procedure
2.1. Raw materials
In this work, quasi-spherical graphite with purity of 99.9% and the average diameter of
17 um (Furunda co. Ltd, China) was used as raw powder for the deposition of nickel
alloy and copper. Analytical reagents and deionized water were used to prepare the
electroless plating solution.

2.2. Pretreatment of graphite

Prior to electroless plating, it is essential to carry out the surface pretreatment of graphite.
The pretreatment technique involved the following steps: Firstly, the graphite particles were
stirred in sodium hydroxide solution (200 g/L) at 90°C–100°C for 1 h to remove organics
on the surface, and cleaned with deionized water. After that, the degreased graphite
particles were stirred in 20 vol.% HNO3 solution for 1 h in order to roughen the surface
of graphite particles. Afterwards, the rough graphite particles were filtered off and washed,
and then immersed in sensitization solution (10 g/L SnCl2, 20 ml/L HCl) for 10 min and
washed with deionized again. Finally, the graphite particles were put into activation
solution (0.1 g/L PdCl2, 5 ml/L HCl) and stirred for 10 min.

2.3. Preparation of copper/nickel-coated graphite powder

The pretreated graphite was successively coated with nickel and copper by electroless
plating to prepare Cu-Ni double-layer coated graphite powder. The plating conditions and
detailed compositions of the depositing bath are listed in Table 1. To obtain different
plating thicknesses, the different amounts of activated graphite particles were added into
plating solutions with same volume and concentration. Therefore, the volume of Ni-P
coating can be effectively controlled by the amount of spherical graphite in the plating
4 Y. YUAN ET AL.

Table 1. The composition of solution and parameters of the electroless plating.

Electroless nickel plating Electroless copper plating
Chemical compounds Concentration Chemical compounds Concentration
NiSO4•6H2O (g/L) 25 CuSO4•5H2O (g/L) 30
NaH2PO2•H2O (g/L) 20 KNaC₄H₄O6•4H₂O (g/L) 25
Propionic acid (ml/L) 10 Glyoxylic acid (ml/L) 10
Lactic acid (ml/L） 30 EDTA•2Na (g/L) 25
NH3•H2O (ml/L) 50–80 NaOH 30
Stability (ml/L) 10–15 Stability (ml/L) 10–15
pH 4–5 pH 11–13
Temperature (°C) 65–70 Temperature (°C) 40–55

bath. The Ni-coated graphite particles with different plating thickness (the volume fraction
of Ni-P coating is 10 vol.%, 15 vol.%, 20 vol.%, respectively) were designated as GN10,
GN15, GN20, respectively. The Ni-P coated graphite particles were rinsed carefully after
Ni plating and then directly used for copper plating. As comparison, copper was also
deposited on the graphite particles without Ni-P coating. After plating, the copper/nickel
double-layer coated graphite composite powders were washed with deionized water to
neutral, dried at 80 °C for 6 h and reduced in hydrogen atmosphere at 450 °C for 30 min.

2.4. Preparation of graphite/copper composites

The samples were fabricated by spark plasma sintering (FCT D25/3, FCT Systeme
GmbH Co., Ltd., Germany) with the sintering pressure of 35 MPa and sintering
temperature of 850–950 °C. In the end, the graphite/copper composites were obtained
from different graphite particles without Ni-P coating and with Ni-P coating, respec-
tively, donated as G/Cu, GN10/Cu, GN15/Cu, GN20/Cu composites. The chemical
compositions of these composites are listed in Table 2.

2.5. Characterization
The chemical elements of the composites were analyzed by inductively coupled plasma-
optical emission spectroscopy (ICP-OES, iCAP 7000, Thermo Fisher Scientifific Co., Ltd.,
USA). The oxygen content was determined in a nitrogen and oxygen analyzer (TCH-600,
Britain). The Archimedes’ principle was used for measuring the density and relative
density of graphite/copper composites. The compressive strength measurements were
performed using a MicroMet 5104 tester (BUEHLER, America). The results were mea-
sured through the average of three parallel tests on cylinder specimens (ϕ5 mm × 5 mm)
by using an electronic universal testing machine. The hardness tests were conducted on the
surface of the composites by a Brinell hardness tester with an indentation ball of 2.5 mm

Table 2. The chemical composition (wt. %) of the designed graphite/copper composites.

Specimens composition (vol.%) C Ni P Cu O
G/Cu C40Cu60 14.71 0 0 84.26 1.07
GN10/Cu C40Ni-P4.5Cu55.5 14.47 3.41 0.66 81.24 0.21
GN15/Cu C40Ni-P7Cu53 15.01 4.36 1.27 79.81 0.09
GN20/Cu C40Ni-P10Cu50 15.07 6.36 1.82 76.02 0.05
 COMPOSITE INTERFACES 5

under a load of 62.5 Kg and a dwell time of 30 s. The results were averaged to estimate the
hardness of the composites by testing five parallel positions for each composition.
The phase composition of graphite/copper powders and composites were character-
ized by X-ray diffraction (RIGAKU-3014, Japan). The morphologies of powders, com-
posites, fracture surfaces were characterized by scanning electron microscopy (FEI,
Nova NanoSEM 230) equipped with energy dispersive spectrum (EDS). The micro-
structure of the composite powders and composite bulk were characterized by trans-
mission electron microscope (JEM-2100F, Japan). Selected area electron diffraction
(SAED) of the interface was carried out.

3. Results and discussions

3.1 Characterization of Cu/Ni-coated graphite particles
SEM photographs of Ni-coated and uncoated graphite particles are shown in Figure 1.
The raw graphite particles are nearly ellipsoidal in shape, and the surface of the graphite
particles is smooth and flat. After electroless nickel plating, the graphite particles are
coated with a uniform nickel coating. As shown in Figure 1(b–d), when nickel content
increases from 10 vol.% to 20 vol.%, the nickel coating is increasingly dense and
completed. It can be observed from Figure 1(d) that the nickel coating covers on the

Figure 1. SEM photographs of Ni-coated graphite powders with different Ni content: (a) 0 vol.%, (b)
10 vol.%, (c) 15 vol.% and (d) 20 vol.%.
6 Y. YUAN ET AL.

graphite particles uniformly and completely. This is attributed to the mechanism that
nickel coating tends to grow in the form of layers during electroless nickel plating.
Therefore, graphite can be well coated with a small amount of nickel content.
SEM photographs of Cu-coated graphite powder and Cu/Ni-coated graphite powder
are shown in Figure 2. It could be clearly observed that the copper plating layer is
composed of spherical copper particles. In addition, the size of copper particles on the
Ni-coated graphite powder is much smaller than that on the graphite powder without
nickel coating, and the surface of Cu/Ni-coated graphite powder is also more homo-
geneous and denser. The reasons can be presented as follows. Electroless copper plating
is a process of nucleation and growth of copper crystal. Specifically speaking, copper
ions are firstly reduced on active palladium sites and the reduced copper can further
catalyze the reduction of copper ions as new catalytic active sites. In another word, once
copper is precipitated, it will preferentially grow on the surface of the copper coating.
The catalytic active sites on the surface of graphite without nickel coating are limited,
which causes the copper coating to grow in the form of particles. Compared with
graphite without nickel coating, the nickel atoms as catalytic active sites can catalyze the
deposition of copper atoms on the graphite surface. Therefore, the copper atoms
nucleate and grow on the nickel coating, forming a dense and uniform layer of copper
coating. In general, pre-electroless nickel plating on graphite surface is beneficial to
obtain a compact and uniform copper coating.
Details of Cu-coated graphite powder and Cu/Ni-coated graphite (GN/Cu) powder which
were heat treated in hydrogen at 450°C for 30 min are shown in Figure3(a–c). Through cross-
section morphology of nickel-copper coated graphite particle as expressed in Figure 3(a–b), it
can be easily observed that the Cu-Ni deposited on graphite surface exhibited the densifica-
tion and homogenization. It would be beneficial for the sintering and strengthening the
interface between graphite, nickel and copper matrix in the composites. According to the
EDS results in Figure 3(b), it can be seen that there are obvious interfaces between graphite
(red curve), Ni-P coating (dark blue and green curve) and copper coating (light blue curve). It
can be deduced that there is little diffusion between these elements before sintering.
Meanwhile, a small amount of Ni phase and Ni3P phase can be observed in XRD patterns
of GN/Cu powders. When the nickel-copper-coated graphite was heat treated at 450°C for 30

Figure 2. SEM photographs of Cu-coated graphite powders: (a) Cu-coated graphite powder, (b) Cu/
Ni-coated graphite powder.
 COMPOSITE INTERFACES 7

Figure 3. Microstructure details of Cu/Ni-coated graphite powders and composites: (a) Cross section
morphology of Cu/Ni-coated graphite powder, (b) and (d) Interface line scanning in Cu/Ni-coated
graphite powders and composites, (c) and (e) XRD patterns of Cu/Ni-coated graphite powders and
composites.

min, nickel would react with phosphorus to generate phosphide (Ni3P). It is also in
accordance with that reported in Ref [28].

3.2 Microstructure of graphite/copper composites

SEM photographs of graphite/copper composites sintered at 900 °C are shown in Figure 4.
Figure 4(a) demonstrates the microstructure of composites without Ni-P coating. The
graphite particles are unevenly distributed throughout copper matrix and some particles
agglomerate in copper matrix (marked by circle). However, the Ni coating anchored on the
graphite surface can serve as spacer to prevent the graphite from aggregating and restacking
during the sintering process, which would lead to a homogeneous distribution of graphite
in the final composites. As shown in Figure 4(b–d), when the Ni coating is introduced, not
only the graphite particles distribute evenly in composites, but also a continuous near-net-
shaped copper matrix is formed.
In order to analyze the role of pre-coated nickel on the surface of graphite, the interface of
G/Cu (the graphite/copper composites without nickel coating) and GN/Cu (the graphite/
copper composites with nickel coating) composites were studied. EDS line-scan results of
GN10/Cu (C40Ni-P4.5Cu55.5) composites are given in Figure 3(d). It can be observed that the
mutual diffusion of the nickel element (dark blue-green curve) and carbon element
(red curve) as well as the mutual diffusion of the nickel element and copper element
(light blue curve) occur at the interface of nickel coatings. XRD analysis was used to further
identify the phase and the result is shown in Figure 3(e). Compared with G/Cu composite, the
XRD analysis shows the shift of characteristic peaks of copper to a higher angle due to the
introduction of Ni coating, and the angle shift is more obvious with the increase of Ni content
8 Y. YUAN ET AL.

Figure 4. SEM photographs of graphite/copper composites with different Ni content: (a) 0 vol.%; (b)
4.5 vol.%; (c) 7.0 vol.%; (d) 10.0 vol.%.

from 0 to 10 vol.%. This is ascribed to the fact that more Ni element is dissolved into the
copper matrix with the increase of Ni content. In addition, X-ray diffraction patterns reveal
that the characteristic peaks of Ni and Ni3P phases are more obvious and stronger
after sintering (compared with Figure 3(c)). These results indicate that the interface of Cu-Ni-
Ni3P and graphite-Ni-Ni3P exists in the GN/Cu composites.
For the purpose of comprehensive and more detailed evaluation of the interface between
Cu matrix and graphite in the G/Cu composites and GN10/Cu composites, TEM was used
to analyze the microstructure of the G/Cu composites and GN10/Cu composites as shown
in Figure 5. Figure 5(a) illustrates the interface morphology of G/Cu composites. It can be
clearly found that the interface cracks exist along the interface of G/Cu composites. These
cracks can easily extend when the composites are subjected to an applied normal
load, reducing greatly the mechanical properties. Such phenomenon indicates a poor
interfacial interaction between Cu matrix and graphite because of neither wetting nor
reaction in Cu-C system [29]. Figure 5(b) demonstrates that the graphite appears to be
well bonded to the Cu matrix and cracks are not observed along the interface. In addition,
an interlayer is visible between graphite particle and Cu matrix. The SAED patterns of the
interfacial layer at position B are in good agreement with those of Ni crystal and Ni3P (seen
in Figure 5(c)). Furthermore, the element distribution near the interface in GN10/Cu
composites was analyzed by EDS, marked as A, B, and C in Figure 5(b). Figure 5(c)
shows relative analysis of the composition in these three areas. The results indicate that the
 COMPOSITE INTERFACES 9

Figure 5. (a) TEM photograph of interface in graphite/Cu composites without Ni coating, (b) TEM
photograph of interface in the CN10/Cu composites, (c) SAED pattern of the area marked B in (b)
and (d) the EDS spectra of the marked A,B and C in (b).

points A, B, and C in Figure 5(b) are graphite, nickel transition layer, and copper
matrix, respectively. Meanwhile, good interfacial bonding can be observed between Cu
matrix and graphite in HRTEM images as shown in Figure 6. According to inverse

Figure 6. (a) HRTEM photographs of the interface in GN10/Cu composites, (b), (c) and (d) inverse
Fourier-transformed images for the corresponding areas.
10 Y. YUAN ET AL.

Fourier-transformed images (seen in Figure 6(b–d)), it can be judged that the interface in
GN10/Cu composites includes graphite phase area, Ni3P phase, Ni phase area (nickel
coating area) and Cu phase area. It is worth noting that nickel atoms diffuse into copper
lattice and generate substitutional solid solution. As a result, copper lattice distortion also
occurs in the morphology of matrix in Figure 6(b). The spacing of (111) crystal plane
changes from 0.208 nm (normally parameter) to 0.202 nm. Meanwhile, the lattice fringe
spacing of Ni also becomes larger than the crystal plane spacing of Ni (111) in the PDF
card because of the diffusion of carbon and copper into Ni coating. Therefore, these
results demonstrate clearly good interfacial bonding between Cu matrix and graphite in
GN10/Cu composite. In addition, the interface actually contains two sub-interfaces: Cu-Ni-
Ni3P interface and graphite-Ni-Ni3P interface.

3.3 Modifying mechanism of nickel in Cu/Ni-coated graphite composites

The diffusion mechanism of the interface of GN10/Cu composite is illustrated in Figure 7.
The diffusion processes can be divided into three stages. At first (before sintering), there is
almost no diffusion between elements as shown in Figure 3(a–c). The interface of GN10/Cu
composites is composed of two kinds of interfaces as the schematic shown in Figure 7(a). The
interface A is graphite/nickel coating interface and the interface B is nickel coating/copper
matrix interface. During the sintering process at t1 stage, the reaction of Ni atoms
with P atoms generates compounds Ni3P (actually, a small amount of Ni3P can generate at
heat-treated process). It is clearly demonstrated in Figure 7(b) that carbon atoms and nickel
atoms diffuse interstitially in region A. However, nickel atoms and copper atoms are easy to
form the substitutional solid solutions, resulting in vacancy diffusion in region B [30].
After the completion of the sintering process, as shown in Figure 7(c) (as discussed in
Section 3.1), the diffusion of nickel atoms and carbon atoms in region A forms the interface
of graphite-Ni-Ni3P. In addition, the diffusion of copper atoms and nickel atoms in the region

Figure 7. The diffusion mechanism with three stages at the interface of GN10/Cu composites: (a)
Initial stage, (b) t1 stage and (c) final stage.
 COMPOSITE INTERFACES 11

B forms the interface of Cu-Ni-Ni3P. Correspondingly, composite interface is composed of

graphite-Ni-Ni3P interface and Cu-Ni-Ni3P interface. The interfacial bonding between
graphite and Cu matrix transforms from mechanical-physical bonding to mechanical-
chemical and diffusion bonding due to the introduction of Ni-P coating.

3.4 Mechanical properties of graphite/copper composites

3.4.1 Effect of sintering temperature
GN10/Cu composites were selected for studying the effect of sintering temperature on
mechanical properties of the composites. Table 3 demonstrates the obvious effect of sintering
temperature on mechanical properties of the GN10/Cu composites. Sintered density, relative
density, compressive strength and hardness increase noticeably with the increase of sintering
temperature from 850 °C to 900 °C. However, when sintering temperature increases to 950 °C,
the mechanical performances deteriorate. Therefore, the best mechanical properties of com-
posites can be achieved when the sintering temperature is 900 °C.
The transformation of mechanical properties as a factor of sintering temperature for
GN10/Cu composites can be explained as follows. The composite interface is composed of
two sub-interfaces, Cu-Ni-Ni3P interface and graphite-Ni-Ni3P interface. During the
sintering process, the inter-diffusion of (Ni+Ni3P)-copper benefits the good bonding of
copper-Ni-Ni3P coating interface. Meanwhile, the carbon atoms can diffuse into the nickel
coating, which is beneficial to the combination of graphite-Ni-Ni3P interface. These inter-
diffusions are promoted with the increase in temperature. In addition, copper-nickel
substitutional solid solution which contributes to elevate the strength of metal matrix can
be generated through inter-diffusion. The inter-diffusion is poorer at 850 °C than that at
900 °C, resulting in the poor mechanical properties of composites at 850 °C.
The degradation of mechanical properties for GN10/Cu composites at 950 °C can be
explained as follows. On one hand, the decrease of mechanical properties of the composites
may be related to the appearance of copper liquid phase during sintering at 950°C. The
coefficient of thermal expansion of copper (16.5 × 10−6 K−1) is too different from that of
graphite (1 × 10−6 K−1 on the X-Y orientation and 26 × 10−6 K−1 on the Z orientation).
Because of the huge thermo-mismatch, the thermal stress generates on the graphite particles
as a compressive stress in the melting process and a tensile stress in the solidification process
that results in separating between copper matrix and graphite particles [22]. On the other
hand, during the sintering process, the gaps among powders constantly shrink and spher-
oidize through grain boundary diffusion, and then discharge from the green body. However,
the relationship between grain growth and material densification is competitive. The tem-
perature is exceedingly high so that grain boundary migrates quickly and separates early from
the pores. Finally, the pores that are not exhausted can transform into closed pores, which
would lead to the degradation of mechanical properties of GN10/Cu composites at 950 °C.

Table 3. Properties of sintered GN10/Cu composites at different temperature.

Sintered density Relative density
Temperature (g/cm3) (%) Compressive strength(MPa) Hardness(HB)
850°C 6.12 ± 0.03 99.82 ± 0.15 262 ± 4 57.6 ± 1.9
900°C 6.13 ± 0.02 99.91 ± 0.13 291 ± 3 61.8 ± 2.1
950°C 5.92 ± 0.09 96.48 ± 0.21 283 ± 5 47.2 ± 2.4
12 Y. YUAN ET AL.

In summary, the better sintering temperature for GN10/Cu composites is 900 °C, at
which the composites exhibit the best properties.

3.4.2 Effect of Ni-P content

Figure 8 shows the effect of Ni volume fraction on the mechanical properties of the
composites sintered at 900 °C. It can be seen from Figure 8(a) that the hardness (from
40.1 HB to 67.8 HB) and compressive strength (from 226 MPa to 314 MPa) increase
significantly with increase of Ni-P content from 0 vol.% to 10 vol.%. The reasons can be
explained as follows. By means of electroless nickel plating on the graphite, the compo-
sites can not only generate solid solution strengthening from nickel coating but also
have higher strength at the interface as discussed above. As shown in Figure 8(b), the
relative density of the composites has a marked enhancement with increase of Ni-P
content from 0 vol.% to 4.5 vol.% and the maximum of relative density reaches up to
99.91% when the Ni-P content is 4.5 vol.%. As the nickel content increase continuously,
the relative density remains above 99%. The reasons can be explained as follows. On one
hand, the agglomeration of graphite particles (seen in Figure 4(a)) could influence the
thermal conduction of the composite, influencing the densification during the sintering
process. When nickel coating is introduced, the graphite particles distribute evenly in
composites and a continuous near-net-shaped copper matrix is formed (seen in Figure 4
(b–d)). On the other hand, the presence of nickel coating contributes to the improve-
ment of interfacial bonding and then impedes the formation of micropores during
sintering process. Consequently, the mechanical properties of the composites with
nickel coating are much better than those without nickel coating. The composites
with 10 vol.% Ni-P addition exhibit excellent mechanical properties with the hardness
of 67.8 HB, compressive strength of 314 MPa and relative density of 99.8%, respectively.
SEM photographs of the fracture surface of the composites are presented in Figure 9.
Figure 9(a) shows obviously that the fracture surface of G/Cu composites is tortuous and
possesses the characteristic step distribution. Two types of fracture surface are observed: the
graphite particle is separated from Cu matrix or Cu matrix is broke away from the graphite
particles. Meanwhile, the fracture surfaces show increasingly smooth morphology with
increasing the addition of Ni-P. According to the Griffith theory of fracture, stress

Figure 8. Mechanical properties of graphite/copper composites with different Ni content: (a) Brinell
hardness and Compressive strength and (b) Sintered density and Relative density.
 COMPOSITE INTERFACES 13

Figure 9. SEM photographs of the fracture surfaces with different Ni content: (a) 0 vol.%; (b) 4.5 vol.%;
(c) 7.0 vol.%; (d) 10.0 vol.%.

concentrations easily occur around the defects in material and finally lead to the development
of cracks [31]. Due to the poor wettability of copper and graphite, the interface of the G/Cu
composites is mainly combined in the form of mechanical meshing, which makes the cracks in
the interface become the main defects. In addition, the sizes of defects in the interface are
larger than the defects (such as pores, dislocations, etc.) in the composites. Therefore, during
the compression test, the crack propagates easily along the main defects and forms a fracture
with the characteristic of step. However, the introduction of the Ni coating greatly improves
the interfacial bonding of the composites, so that the number and size of the defects are much
smaller than that of G/Cu composites. Therefore, during the compression test, the cracks
directly pass through the copper matrix and graphite, forming a smoother flat fracture surface.
Based on these results, it can be summarized that the insertion of Ni coating can promote the
properties of graphite/copper composites.

4. Conclusion
In this paper, graphite was coated with nickel to improve the wettability at the interface.
Then, the Ni-coated graphite was deposited with copper to replace copper powder
addition. The obtained double-layer particles were directly compressed and sintered in
SPS system. The interfacial characterizations and modification mechanism of nickel
coating in the composites were analyzed. The effects of the sintering temperature and
14 Y. YUAN ET AL.

the Ni volume fraction on the mechanical properties and microstructure of composites

were also systematically investigated. The conclusions are drawn as follows:

(1) The introduction of Ni coating was beneficial to electroless copper plating. Compared
with the graphite powder without nickel coating, the surface of Cu/Ni-coated graphite
powder is more homogeneous and denser. In addition, compared with the graphite/
copper composites without Ni-P coating, the microstructure of the composites also
became denser, finer and more homogeneous.
(2) The introduction of Ni-P coating transformed the copper–graphite interface into
copper-Ni-Ni3P interface and graphite-Ni-Ni3P interface. The interface trans-
formed from mechanical-physical bonding to mechanical-chemical and diffusion
bonding, greatly improving the wettability between graphite and Cu matrix.
Therefore, the Cu-Ni double-layer coated graphite composites exhibited higher
relative density and better mechanical properties than those without Ni coating.
(3) The better sintering temperature for graphite/copper composites with Ni-P
coating was 900°C. At this temperature, the composites exhibited superior
performance. Meanwhile, the hardness, compressive strength and relative density
of obtained composites increased with increase of Ni-P content and reached
a maximum value of 67.8 HB, 314 MPa, 99.8% with 10 vol.% Ni-P content.

Acknowledgments
A project (Grant No.2016YFB0301402) supported by the national key research and development
program of china is gratefully acknowledged.

Disclosure statement
No potential conflict of interest was reported by the authors.

References
[1] Prasad BK. Sliding wear behaviour of bronzes under varying material composition,
microstructure and test conditions. Wear. 2004;257:110–123.
[2] Ding T, Chen GX, Zhu MH, et al. Influence of the spring stiffness on friction and wear
behaviours of stainless steel/copper-impregnated metallized carbon couple with electrical
current. Wear. 2009;267:1080–1086.
[3] Moustafa SF, El-Badry SA, Sanad AM, et al. Friction and wear of copper-graphite
composites made with Cu-coated and uncoated graphite powders. Wear.
2002;253:699–710.
[4] Guang-Yang HU. Application research of seal technologies for aeroengine. Aeroengine.
2012; 38:1–4.
[5] Devincent SM, Michal GM. Improvement of thermal and mechanical properties of
graphite/copper composites through interfacial modification. J Mater Sci. 1993;2:323–331.
[6] Zhou W, Yi M, Peng K, et al. Preparation of a C/C–cu composite with Mo2C coatings as
a modification interlayer. Mater Lett. 2015;145:264–268.
[7] Dong R, Cui Z, Zhu S, et al. Preparation, characterization and mechanical properties of
Cu-Sn alloy/graphite composites. Metall Mater Trans A. 2014;45:5194–5200.
 COMPOSITE INTERFACES 15

[8] Paul R, Dai L. Interfacial aspects of carbon composites. Compos Interfaces. 2018;
25:539–605.
[9] Yang MJ, Zhang DM, Gu XF, et al. Effects of SiC particle size on CTEs of SiCP/Al
composites by pulsed electric current sintering. Mater Chem Phys. 2006;99:170–173.
[10] Jiang JT, Zhen L, Xu CY, et al. Microstructure and magnetic properties of SiC/Co
composite particles prepared by electroless plating. Surf Coat Technol.
2006;201:3139–3146.
[11] Guo MLT, Tsao CYA. Tribological behavior of aluminum/SiC/nickel-coated graphite
hybrid composites. Mater Sci Eng A. 2002;333:134–145.
[12] Li Q, Zeng G-Z, Zhao W-F, et al. Preparation and characterization of nickel-coated
graphite nanosheets. Synth Met. 2010;160:0–202.
[13] Ip SW, Sridhar R, Toguri JM, et al. Wettability of nickel coated graphite by aluminum.
Mater Sci Eng A. 1998;244:31–38.
[14] Yang W, Fu Y, Xia A, et al. Microwave absorption property of Ni-Co-Fe-P-coated flake
graphite prepared by electroless plating. J Alloys Compd. 2012;518:6–10.
[15] Chen J, Ren S, He X, et al. Properties and microstructure of nickel-coated graphite flakes/
copper composites fabricated by spark plasma sintering. Carbon. 2017;121:25–34.
[16] Wang Y, Gao Y, Li Y, et al. Research on nickel modified graphite/Cu composites interface.
Surf Coat Technol. 2017;328:70–79.
[17] Li SJ, Song MJ, Xia YL, et al. Wettability of graphite/Ni plus Cr system. Key Eng Mater.
2008;368:1621–1624.
[18] Zhao H, Lei L, Hu W, et al. Friction and wear behavior of Ni-graphite composites
prepared by electroforming. Mater Des. 2007;28:1374–1378.
[19] Tang Y, Yang X, Wang R, et al. Enhancement of the mechanical properties of
graphene-copper composites with grapheme-nickel hybrids. Mater Sci Eng A.
2014;599:247–254.
[20] Wang Y, Gao Y, Sun L, et al. Effect of physical properties of Cu-Ni-graphite composites on
tribological characteristics by grey correlation analysis. Results Phys. 2016;7:263–271.
[21] Wozniak J, Kurtycz P, Broniszewski K, et al. Properties of alumina matrix composites
reinforced with nickel-coated graphene. Mater Today. 2015;2:376–382.
[22] Liu Q, He X-B, Ren S-B, et al. Thermophysical properties and microstructure of graphite
flake/copper composites processed by electroless copper coating. J Alloys Compd.
2014;587:255–259.
[23] Pan Y, He X, Ren S, et al. High thermal conductivity of diamond/copper composites
produced with Cu–zrC double-layer coated diamond particles. J Mater Res. 2018;53:1–11.
[24] Yang C, Kang LM, Li XX, et al. Bimodal titanium alloys with ultrafine lamellar eutectic
structure fabricated by semi-solid sintering. Acta Mater. 2017;132:491–492.
[25] Liu LH, Yang C, Wang F, et al. Ultrafine grained Ti-based composites with ultrahigh
strength and ductility achieved by equiaxing microstructure. Mater Des. 2015;79:1–5.
[26] Liu LH, Yang C, Kang LM, et al. Equiaxed Ti-based composites with high strength and
large plasticity prepared by sintering and crystallizing amorphous powder. Mater Sci Eng
A. 2016;650:171–182.
[27] Sule R, Olubambi PA, Sigalas I, et al. Effect of SPS consolidation parameters on submicron Cu
and Cu-CNT composites for thermal management. Powder Technol. 2014;258:198–205.
[28] Younan MM, Aly I, Nageeb MT. Effect of heat treatment on electroless ternary
nickel-cobalt-phosphorus alloy. J Appl Electrochem. 2002;32:439–446.
[29] He J, Zhang H, Yang Z, et al. Effect of boron addition on interface microstructure and
thermal conductivity of Cu/diamond composites produced by high temperature-high
pressure method. Phys Status Solidi. 2014;211:587–594.
[30] Wu G, Zhang Q, Xue Y, et al. Effects of particle/matrix interface and strengthening
mechanisms on the mechanical properties of metal matrix composites. Compos
Interfaces. 2014;21:415–429.
[31] Kierfeld J, Vinokur V. Crack propagation, arrest and statistics in heterogeneous materials.
J Stat Mech-Theory Exp. 2008;2008:4–11.