Composites: Part B 44 (2013) 698703

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

Thermal properties of aluminumgraphite composites by powder metallurgy

J.K. Chen , I.S. Huang
Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei 10608, Taiwan, ROC

a r t i c l e

i n f o

Article history:
Received 12 November 2011
Received in revised form 15 January 2012
Accepted 24 January 2012
Available online 2 February 2012
Keywords:
A. Metalmatrix composites (MMCs)
B. Anisotropy
B. Thermal properties
E. Sintering

a b s t r a c t
1090 vol.% of ake graphite is combined with aluminum powders to form aluminumgraphite composites via vacuum hot pressing process. The results show that the relative density of powder composites
achieves up to 99% for composites containing 1090 vol.% graphite. With the increase of ake graphite
from 10 to 90 vol.% in the composites, thermal conductivity increase from 324 to 783 W/m K; the coefcients of thermal expansion (CTE) in direction parallel to basal planes of graphite akes decrease from
16.9 to 2.5 ppm/K, and the CTE perpendicular to basal plane decreases from 15.2 to 10.1 ppm/K. The
parallel arrangements of graphite akes and aluminum lead the thermal conductivity values of composites to agree well with parallel model estimations. The CTE of composites in a-axis agree with rule of mixture estimation representing proportional contribution of the two phases. Along the c-axis of graphite in
composites, the CTE are consistent with Turner model estimations indicating that the graphite ake could
absorb the expansion from the aluminum phase.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Thermal management material has been of signicance in the
electronic industry [1]. The development of electronic devices with
higher calculating speeds within a more compact size leads to
more heat generation per device. In order to meet thermal dissipation requirements for electronic packaging applications, materials
with high thermal conductivity and low thermal expansion must
be developed [2].
Traditional electronic packaging materials are mostly pure metals that have excellent thermal conductivity, e.g. Cu, Al, Au and Ag.
However, these metals usually also have high coefcients of thermal expansion which are much higher than that of semiconductor
device to be packaged. Besides, high density and costs are also
problems for the applications of these metals. Recently, development of ceramic (e.g. BeO [3], AlN [4], Al2O3 and SiC [5]) and metal
matrix composites (e.g. CuMo and CuW [6]) has been quickly
replacing the uses of monolithic metals for thermal dissipation in
electronic packaging [7]. Among these, Al-based metal matrix composites, such as AlSiC [8] and Algraphite [9], has matched coefcient of thermal expansion and good mechanical properties, but
the poor metallization of ller phase could lead to heat damage
[10] due to thermal mismatch strain [11].
The pressure inltration of the liquid metal into the ceramic
preform was developed [12,13] to improve the wettability
between ller and matrix alloy [14]. Composites containing higher
Corresponding author. Address: 1, Sec. 3, Zhong-Xiao E. Rd., Taipei 10608,
Taiwan, ROC. Tel.: +886 2 2771217x2763; fax: +886 2 27317185.
E-mail address: jkchen@ntut.edu.tw (J.K. Chen).
1359-8368/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2012.01.083

volume percentage of llers can also be fabricated using liquidbased process. However, Al4C3 phase is often found to form on
the llers by reacting with liquid metals in either aluminum
graphite [15] or aluminumSiC [8] composites. The Al4C3 phase
is detrimental to the composites by greatly reducing both their
thermal conductivity and mechanical properties.
To avoid the formation of Al4C3 phase, powder metallurgy route
is employed in current study to fabricate Algraphite composites
instead of conventional liquid-based process. Although the characteristic plate-shaped graphite could make it a less ideal ller from
mass production point of view, proper molding can be designed
to align the graphite akes. The anisotropic physical properties
can also be taken advantage by aligning the basal planes of graphite
akes in direction consistent with heat transfer. For example,
pulsed electric current sintering process was employed to make
aluminumgraphite ber composites with thermal conductivity
as high as 600 W/m K [16] and coefcient of thermal expansion
below 20 ppm/K. Therefore, high thermal conductivity could be
achieved in the same time while the coefcient of thermal expansion is controlled.

2. Experimental procedures
Commercially available aluminum powders (99.9% purity;
d50 = 35 lm) and natural ake graphite (graphitization degree
98%; d50 = 550 lm and thickness = 1030 lm) were mixed using
dry process. 1090 vol.% of ake graphite is added in the composite
materials. The ake graphite has its surface parallel to the basal
plane and thickness parallel to the c-direction as shown in Fig. 1.

J.K. Chen, I.S. Huang / Composites: Part B 44 (2013) 698703

Fig. 1. XRD analysis of ake graphite showing ake surface parallel to the basal
plane.

The mixtures of aluminum and ake graphite were lled in a

graphite mold for hot press. The ake graphite stacks naturally
by layer into the mold with tapping while lling. Hot press process
was then performed at 913 K and a pressure of 60 MPa for 1 h
under 2  102 torr vacuum. After hot pressing, different samples
can be cut from desired directions so that thermal properties are
measured along interested directions.
Microstructures of sintered materials were examined with optical microscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). And the density of composite was measured using
Archimedes method. Aluminumgraphite composite disks (
2.7 mm  3 mm) were carbon-coated for thermal diffusivity measurement. Thermal diffusivity was measured via laser ash technique using a NETZSCH LFA447 NanoFlashTM thermal constant
analyzer. The measurements were performed such that orientation
of heat dissipation was parallel to the basal plane of graphite akes.
The heat capacity of composite was measured by differential scanning calorimeter (Perkin Elmer Pyris) at 300 K. Thermal conductivity is thus obtained by multiplying composite density, specic heat,
and thermal diffusivity of the composites. Coefcients of thermal
expansion were measured from room temperature to 373 K using
NETZSCH DIL 402C dilatometer and the shape of the specimen
was 10 mm  5 mm  5 mm.

3. Results and discussion

3.1. Microstructures
Fig. 2 shows the microstructures of Algraphite composites
with different graphite percentage. The brighter phase is aluminum and dark region is nature ake graphite. No signicant pores
exist in the interface between aluminum and graphite in Fig. 2ag
or composites containing up to 70 vol.% graphite. The use of hot
pressing temperature close to melting point of aluminum and
pressure under vacuum atmosphere apparently provide adequate
wettability for graphite to sinter with aluminum.
Increased pores can be observed in samples containing higher
than 80 vol.% graphite or Fig. 2hi. With increasing graphite, the
bonding phase or aluminum decreases and becomes harder to
infuse among graphite akes. Furthermore, it is observed that the
graphite akes are bent severely in Fig. 2i containing 90 vol.%
graphite. The akes are wavy due to the stacking of large amount
of graphite akes with different size under the pressure. The stacking of graphite also closes the passage for aluminum to diffuse
between the akes. Larger pores are thus formed at the graphite
interfaces. These pores apparently will affect the density, thermal
properties, and mechanical properties of composites.

699

Etter et al. [15] reported that aluminum and graphite interface

may form needle-like Al4C3 phase at aluminumgraphite interface
via liquid inltration process. The Al4C3 phase is brittle and tends
to absorb moisture which degrades both the mechanical properties
and thermal conductivity of composites. In this study, Al4C3 was
not observed (Fig. 3). The absence of the Al4C3 phase is also
conrmed by XRD analysis in Fig. 4, while the graphite peak
increases with amount of ake graphite.
There are two reasons that the current process suppresses
formation of Al4C3 phase. Mizuuchi et al. [17] demonstrated that
surface damages of llers by direct contact with molten aluminum
cause the reductions of materials properties. The hot press temperature of 913 K is lower than the melting point of aluminum
(933 K). The formation of Al4C3 can thus be avoided. Furthermore,
ake graphite with nearly 100% graphitization degree [18] is
employed in current study which is higher than those used in
the literature [15,19]. The more stable ake graphite with larger
at surface has lower tendency for Al4C3 phase formation.
Fig. 5 shows the theoretical and experimental density of aluminumgraphite composites. The density apparently decreases linearly with increase of graphite content except at graphite content
more than 80 vol.%. Fig. 6 further shows that the relative density
of composites lies mostly at 9799%. From both Figs. 2 and 3,
aluminum and graphite appears to have very good wetting at the
interface. Only very limited amount of pores are observed mostly
at the graphite:graphite interface. The constant <3% open porosity
as shown in Fig. 6 could be caused by the pores within the graphite
akes or graphite damage in sample preparation process.
When the graphite content is higher than 80 vol.%, the theoretical density decreased to below 95%. The pores are observed more
easily in Fig. 2h and i. In these composites, aluminum diffuses with
difculty among the greater number of stacked graphite akes and
results in much higher percentage of pores. From percolation
points of view, this indicates that the graphite akes form close
networks which hinders the infusion of aluminum. The closed
networking of graphite akes are especially signicant when
graphite content is higher than 80 vol.%.

3.2. Thermal conductivity of Algraphite composites

Thermal conductivity of composites is obtained by multiplying
density, specic heat and heat diffusivity as described in Section
2. The thermal conductivity of Algraphite composites with different graphite content are shown in Fig. 7. It is noted that the graphite
akes are arranged such that their basal planes are parallel to the
direction of thermal conduction measurement. Therefore, with
graphite content increasing from 10 to 80 vol.%, thermal conductivity of composites increases from 324 W/m/K to 783 W/m/K. These
values are all much higher than that of pure aluminum (237 W/
m/K) due to the high thermal conductivity of graphite along the
thermal conducting direction, or in current study, the basal planes
of graphite akes. These values are also higher than those reported
by Chang et al. [20] with similar percentage of graphite. Size of
graphite akes and difference in process could combine to cause
the difference. In previous study [20], 100 lm graphite and squeeze
casting process is used. As described in Section 3.1, liquid-based
process could degrade the aluminumgraphite interface. The larger
550 lm graphite akes used in current study are also advantageous
for both a smaller interface thermal resistance and improved connections among the akes. The networks by connecting graphite
akes provide continuous passages for heat transfer. The high thermal conductivity achieved in Al80 vol.% graphite composite conrms the good networking among graphite, even though its
relative density is below 95%. The conductive channel of llers
are also responsible for thermal conduction in a recent work by

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Fig. 2. Optical micrographs of Algraphite composites with (a) 10, (b) 20, (c) 30, (d) 40, (e) 50, (f) 60, (g) 70, (h) 80, and (i) 90 vol.% graphite akes taken along the basal planes.

Fig. 3. SEM micrographs showing no Al4C3 formation in Algraphite composites

containing 50 vol.% graphite (aluminum: lighter region; graphite: dark region).

Baglari et al. [21] on thermal conductivity of ash ash-polymer

composites.
It is further noted that these values are no lower than diamond/
copper composites reported by Yoshida and Morigami [22] where
up to 80 vol.% of diamond is added into copper demonstrating

Fig. 4. XRD spectra of aluminumgraphite composites with different graphite

contents taken with sample surfaces parallel to the ake surface planes.

742 W/m/K thermal conductivity. In the same study, diamond of

larger particle size is also shown to increase thermal conductivity.
On the other hand, in composite containing 90 vol.% graphite,
thermal conductivity drops to 774 W/m/K due to larger amount

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701

Fig. 5. Theoretical and measured density of aluminumgraphite composites.

Fig. 6. Relative density and open porosity of aluminumgraphite composites.

of pores along graphite ake surface. Apparently the greater

increase of porosity outweighs the increase of graphite. The pores
are formed due to the lack of aluminum binding among neighboring graphite which hinders the transfer of heat. Furthermore, the
graphite akes are lack of mechanical strength and are easily bent
to deform which could also deect ow of heat or even damage the
akes as shown in Fig. 2i.
Theoretical calculations are made using parallel model. Parallel
model consider thermal conductivity of composites with parallel
layers of alternating lamellae [23]. Such alternating lamellae are
represented nearly ideally in the case of Algraphite composites.
The effective thermal conductivity, Keff, can be expressed as:

K eff V 1 K 1 V 2 K 2

where K1 and K2 are thermal conductivity, V1 and V2 are the volume

fractions of phase 1 and 2, respectively. Fig. 7 compares the experimental values with those evaluated using parallel model. The measured values apparently agree very well with the predictions except
for composites with over 80 vol.% of graphite. The larger deviation
between the measured and predicted thermal conductivity values
for composite containing 90 vol.% is apparently caused by its sintering density below 93% which reduces the graphite connections.
3.3. Thermal expansion of Algraphite composites
The coefcients of thermal expansion of aluminumgraphite
composites are measured along two directions, namely parallel to
graphitebasalplane(a-axis)andperpendiculartobasalplaneoralong
c-axis. Three models are employed to compare with the measured
coefcients of thermal expansion for current composite system:

where a stands for coefcients of thermal expansion, V is the volume fraction, B is the bulk modulus, G is shear modulus, and the
subscripts M, 1, and 2 refer to the composite, matrix and ller
phase, respectively.
Fig. 8 shows the measured and estimated coefcients of thermal
expansion (CTE) results. The CTE of graphite along a-axis is
1.5 ppm/K and that along c-axis is 8 ppm/K [26,27], and CTE of
aluminum is 23.8 ppm/K. The measured CTE both along and perpendicular to basal plane direction of aluminumgraphite composites decreases with graphite but with very different trends.
The CTEs of composites in directions parallel to the basal plane
of graphite agree reasonably well with rule of mixture as shown in
Fig. 8a. According to the rule of mixture, thermal expansion of
composites constitutes of proportional contributions from both
aluminum and graphite according to their volume percentages.
Therefore, the good approximations of experimental values and
rule of mixture predictions are representative of good interface
bonding between the two phases. The effects of mechanical properties, such as bulk modulus and shear modulus, affect not much
on the CTEs of the composites since Kerner model does not t well
with the measured CTEs. Because aluminum and graphite akes
are both soft in nature, the two phases can expand freely along
the directions parallel to the basal planes. Since the expansion of
aluminum and graphite is additive by proportion, the shear stress
at the aluminumgraphite interfaces must also be minimal without restraining either phase to expand.
On the other hand, the CTEs of composites along c-axis or perpendicular to basal planes are more consistent with Turner model
estimations. Turner model [24] is developed for predicting composites constituted by phases with similar modulus and is based

(a) Rule of mixture

aM V 1 a1 V 2 a2

(b) Turner model [24]:

aM

a1 B1 V 1 a2 B2 V 2
B1 V 1 B2 V 2

(c) Kerner model [25]:

aM a1 V 2 a1  a2


B1 3B2 4G1 2 B2  B1 16G21 12G1 B2

4G1 3B2 4V 2 G1 B1  B2 3B1 B2 4G1 B1 

4
Fig. 7. Comparison of measured and parallel model predicted thermal conductivity.

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containing 1080 vol.% of graphite, the measured thermal conductivity increases from 324 to 783 W/m K. It agrees well with the
parallel model indicating the good interfaces in between aluminum and graphite. Larger amount of pores in aluminum90 vol.%
graphite composites causes its thermal conductivity to deviate toward lower values.
Coefcients of thermal expansion for aluminumgraphite composites decrease with increasing ake graphite. Good bonding
interfaces and low mechanical strengths of aluminum and graphite
cause the coefcients of thermal expansion along the basal plane to
demonstrate a trend close to rule of mixture. The values range from
16.9 to 2.5 ppm/K with increasing graphite content. On the other
hand, the coefcients of thermal expansion in direction perpendicular to the basal planes of graphite in composites demonstrate
comparably higher values mainly due to the low Van der Waal force
along this direction. The measured values ts well with Turner
model indicating that the component of softer graphite direction
provides an absorber for the expansion of aluminum in direction
perpendicular to the basal planes. Therefore the CTE is closer to that
of graphite along c-direction.
The current study demonstrates that the thermal conductivity
and thermal expansion of aluminumgraphite composites can be
controlled easily by the percentage of graphite and orientation
via hot pressing. The process is shown to achieve excellent interface bonding and can avoid detrimental interfacial reactions
between aluminum and ake graphite.
Acknowledgment

Fig. 8. Experimental and theoretical coefcients of thermal expansion for composites containing different percentage of graphite along (a) a-axis and (b) c-axis
direction.

upon zero internal stress assumption. Because graphite ake along

c-axis direction is characteristic of Van der Waal bonds, the modulus along this direction is fairly low and is comparable with that of
pure aluminum. In Fig. 8b, the CTEs decrease rapidly with increasing graphite content to 15 ppm/K and keep at a relatively constant level close to the CTE of graphite in c-direction. It indicates
that the expansion of aluminum is mostly absorbed by graphite
ake in direction perpendicular to basal planes. The expansion of
aluminum becomes omittable for aluminumgraphite composites
containing graphite of nearly all percentage. This still holds true
even for composites with high porosity at very high graphitecontaining composites.
Graphite networks in direction perpendicular to basal planes
appear to absorb the expansion of the binder phase. The pores
among graphite ake networks and weak Van der Waals force in
graphite akes along c-axis can facilitate the absorption.
4. Conclusions
Vacuum hot press in semi-solid liquid state is employed to
make aluminumgraphite composites. Over 98% densication is
achieved for composites containing lower than 70 vol.% of graphite. The interface is observed to bear good bonding characteristics
while no detrimental Al4C3 phase is found to form in composite.
Aluminum acts as the bonding phase between graphite akes.
Porosity increased to over 5 vol.% when ake graphite content is
increased over 80 vol.% due to lack of aluminum diffusion into
graphite networks. The pores are observed to exist at the interfaces
between the graphite akes.
Thermal conductivity of aluminumgraphite composites
increases with increasing amount of graphite. For composites

The authors are grateful for nancial support of this project by

National Science Council of Taiwan under Contract #NSC99-2221E-027-020.
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