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MATERIALS RESEARCH

Processing of carbon nanotube reinforced aluminum composite

T. Kuzumaki, K. Miyazawa, H. Ichinose, and K. Ito
Department of Materials Science, School of Engineering, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
(Received 5 February 1998; accepted 8 June 1998)

Carbon nanotube reinforced aluminum (Al) composites were produced by hot-press and
hot-extrusion methods. The interfacial structure between the carbon nanotube and Al was
examined using a transmission electron microscope (TEM), and the mechanical properties
were measured by a tensile test. TEM observations have shown that the nanotubes in
the composites are not damaged during the composite preparation and that no reaction
products at the nanotubeyAl interface are visible after annealing for 24 h at 983 K. The
strength of the composites is only slightly affected by the annealing time at 873 K,
while that of the pure Al produced in a similar powder metallurgy process significantly
decreases with time. These studies are considered to yield experimental information
valuable for producing high performance composites.

I. INTRODUCTION as graphitic particles or amorphous carbons, so that the

It has been revealed that a carbon nanotube pos- content of the nanotubes was approximately 60 vol %.
sesses not only an extremely high elastic modulus1–3 but The density of the carbon powder was assumed to be
also plasticity.4–7 These findings together with their ex- 2.0 Mgym3 . Al powders (99.99% purity, 40 mm grain
cellent mechanical properties and the predicted chemical size) mixed with 5 or 10 vol % carbon powder (5 or
stability that originates from their seamless cylindri- 10% composite) were stirred in ethanol at 300 rpm for
cal graphitic structure suggest that the nanotube might 0.5 h and immediately dried in a vacuum furnace. The
be suitable as a novel fiber material for composite mixed powder specimens were packed in an Al case.
materials. However, very few studies using nanotubes The cases were preheated for 1.5 h at 873 K in a vacuum
as a composite reinforcement have been carried out of 5.3 3 1021 Pa and then compressed with 100 MPa
experimentally. In conventional carbon fiber/aluminum in steel dies for 60 min. The heating and loading rates
(Al) composites, Al carbide (Al4 C3 ) grows on the prism were 29.1 Kymin and 10 MPaymin, respectively. The
plane of the carbon fiber. This reaction is serious because specimens were reduced by approximately 64%. The
the formation of a sharp notch on the fiber by attack composites were extruded at 773 K into a rod with a
of growing Al4 C3 needles results in a drastic decrease 7 mm diameter (extrusion ratio ­ 25 : 1) at a speed of
in the composite strength.8 In the nanotubeyAl system, 10 mmymin.
however, it is expected that the composite is free from
such a chemical reaction problem and can be fabricated
using a plastic working process.
In general, the mechanical properties of the com-
posites reinforced with whiskers are often affected by
microstructures in the composites, such as reaction phase
at the interface and the aspect ratio or alignment of the
whiskers in the matrix.
We describe here the first attempt to fabricate the
nanotube-reinforced Al composite, focusing on the proc-
essing and the mechanical properties, with the objective
of using nanotubes as an engineering material.

II. PROCEDURES
A. Processing of the composite
Carbon nanotubes are synthesized by carbon dc arc
discharge.9 The carbon powder used in this experiment FIG. 1. Silver sheath and composite wire produced by drawing that
contained both nanotubes and other contaminants such nanotubeyAl composite sheathed in silver.

J. Mater. Res., Vol. 13, No. 9, Sep 1998  1998 Materials Research Society 2445

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 T. Kuzumaki et al.: Processing of carbon nanotube reinforced aluminum composite

TABLE I. Relative density of the specimens produced by powder

metallurgy.

Measured Theoretical Relative

density density density
Specimen/density (Mgym3 ) (Mgym3 ) (%)

Al 2.69 2.70 99.6

NanotubeyAl (5 vol %) 2.50 2.66 94.0
NanotubeyAl (10 vol %) 2.53 2.63 96.2

FIG. 2. TEM image of a tip of the 10% composite specimen heat-

treated for 24 h at 983 K and then fractured for observation.

FIG. 4. Tensile strength of the specimens as a function of annealing

time at 873 K.

FIG. 3. High resolution TEM image of the interfacial structure of the

same specimen as in Fig. 2.

B. Characterization of the composites

1. Interfacial structures
The specimen for the interface observations were
prepared by drawing a silver-sheathed composite.9 The
drawn sheath was heated for 24 h at 983 K within
a sealed quartz tube at 1.3 Pa. The silver matrix was
partially dissolved by nitric acid, and the specimen was
fractured under tensile stress for observations using a
high resolution TEM (JEM-200CX, JEOL).
2. Mechanical properties and microstructures
The relative density of the composites were meas-
ured by the Archimedes method. Tensile test pieces
with a gage length of 15 mm and a diameter of 3 mm
FIG. 5. Elongation of the specimens as a function of annealing time
at 873 K.
were machined from the composites at three processing
stages: as-extruded, 50 h, and 100 h heat-treated at 873 K
at 1.3 Pa. The tensile tests were carried out using an
Instron-type tensile testing machine (Autograph AGS-D
Type-3, Shimadzu) at room temperature with a cross-
head speed of 0.5 mmymin.
Fractured surfaces were observed by a scanning
electron microscope (SEM, S-4200, Hitachi) and TEM.

2446 J. Mater. Res., Vol. 13, No. 9, Sep 1998

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 T. Kuzumaki et al.: Processing of carbon nanotube reinforced aluminum composite

FIG. 6. SEM image of the fractured surface before and after heat treatment for 100 h at 873 K. (a) Pure Al and ( b) 10% composite.

The specimens for the TEM observations were mechani-
cally thinned to approximately 40 mm, and then fractured
under tensile stress.
III. RESULTS
A. Interfacial structures
Figure 1 shows a composite wire produced by the
silver sheath process. As shown in Fig. 2, the nanotubes
are aligned parallel along the longitudinal direction of the
wire by the drawing process and no fractured nanotubes
are observed, which is different when using conventional
carbon fibers. Although some Al beads are observed on
the nanotubes, no contrast corresponding to the reaction
product is found at the present interface which was
heat-treated for 24 h at 983 K as shown in Fig. 3.
The attached microdiffraction pattern in Fig. 3 also
indicates only the halo pattern of Al and diffraction
spots from the nanotubes. No chemical reaction even
at the interface between bent segments of the nanotubes
and the Al matrix is observed. The expected chemical
stability of the nanotube in the Al matrix has been proved
experimentally.
B. Mechanical properties
The relative densities of the specimens are shown in
Table I. The density of a pure Al specimen produced as a
reference is close to the intrinsic density of Al, whereas
the densities of the composites are lower by 4–6% when
compared with the theoretical values for the densities.
The tensile strengths are presented in Fig. 4. In
the as-extruded state, every specimen shows comparable
strength. After the heat treatment, however, the strengths

J. Mater. Res., Vol. 13, No. 9, Sep 1998 2447

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 T. Kuzumaki et al.: Processing of carbon nanotube reinforced aluminum composite
FIG. 7. TEM image of the fractured surface of the 10% composite.
Arrows show the embedded nanotubes in the Al matrix.
of the composites are only slightly affected by the
annealing time at 873 K, while that of the pure Al
significantly decreases with time. The elongation of
the pure Al tends to increase with annealing time at
873 K due to recrystallization and coarsening of the
grains as shown in Fig. 5. The mechanical properties
of the composites reinforced with nanotubes are more
thermally stable than pure Al.
C. Microstructure
Figures 6(a) and 6(b) show the fractured surfaces.
In the composite specimen, a nonhomogeneous structure,
which is made by the coalescence of the carbon powders,
is observed. After heat treatment, the irregularity of the
fractured surface tends to increase and the nanotubes are
scarcely observed in the Al matrix. TEM observations
show the microstructure of the fractured surface where
the rupture occurred in the matrix near the nanotubes,
as shown in Fig. 7. The fractured structure is locally
observed in the composite.
IV. DISCUSSION
An important issue of this study is whether or
not the nanotubes can be applied to the Al matrix
as a reinforcement. These experiments have exhibited
some remarkable results. One is the chemical stability
of the nanotubes in the Al matrix when processed by
powder metallurgy. Contrary to the conventional carbon
fiberyAl composites, TEM observations how that Al
carbide is absent at the nanotubeyAl interface. In the
conventional case, the carbide grows epitaxially on the
prism planes of the carbon fiber. The surface free energy
of the prism planes (4.8 J m22 ) is larger than that of
2448 J. Mater. Res., Vol. 13, No. 9, Sep 1998
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the graphitic basal plane (0.15 J m22 ),10 and it has
been reported that there is an anisotropy of chemical
reactivity in the graphite crystal.11 Therefore, unless the
nanotube is fractured by external stress, the nanotube is
expected to be chemically stable due to its cylindrical
structure that consists of a rolled up graphitic basal
plane. In fact, nanotubes are not damaged during the
composite preparations, and hence, the nanotubes are
suitable for use in an Al matrix composite. The low
chemical reactivity of the nanotubes would contribute to
the thermal stability of the composite strength.
The strength, sc , of the 10% composite was esti-
mated by Kelly–Tyson’s formula12
µ ∂
lc
sc ­ sf Vf 1 2 1 sm0 s1 2 Vf d ,
2l
where sf is the tensile strength of the nanotube esti-
mated from comparison to a commercial high modulus
carbon fiber (­3 GPa), Vf is the volume fraction of the
nanotubes (­0.1), lc is the critical length of a nanotube
in the Al matrix (­0.85 mm), l is the average length
of the nanotubes used in this experiment (­2 mm),
and sm0 is the stress of the Al matrix at the failure
strain of the composite (­40 MPa). The estimated sc is
about 270 MPa. The experimentally obtained strengths
are much lower than this theoretical estimate. A possi-
ble cause of the disagreement is the nonhomogeneous
dispersion of the nanotubes in the Al matrix. The slight
difference in the mechanical properties between the 5%
and 10% composites is possibly due to the same reason.
In addition, the fact that the volume fraction of the
nanotube is less than 10% due to the contaminants and
that not all the nanotubes are aligned along the tensile
axis in the matrix would affect the tensile strength of the
composites. A high purity refinement of the nanotubes,
a homogeneous dispersion method, such as mechanical
mixing, and also the drawing process9 used for the
interface observations are essential factors for fabricating
the nanotube-reinforced composite. At the nanotubeyAl
interface, it is anticipated that the volume contraction of
the Al matrix during the cooling after heat treatment may
contribute to the mechanical adhesion, whereas the effect
of the residual thermal stress that occurred in the matrix
(tensile stress) and in the nanotubes (compressive stress)
must be taken into account in considering the interfacial
mechanical properties.
A further detailed investigation will be required with
a simple model to examine the effect of the distorted
p-electronic structures caused by the cylindrical struc-
ture of the nanotube on the bonding interaction at the
nanotubeyAl interface and on the mechanical properties,
including the reinforcing mechanism of the nanotubes.
IP address: 141.210.2.78
 T. Kuzumaki et al.: Processing of carbon nanotube reinforced aluminum composite
V. CONCLUSION
NanotubeyAl composites have been prepared by hot-
pressing and hot-extrusion. Contrary to conventional
carbon fiberyAl systems, no carbide is observed at the
interfaces in the nanotubeyAl composite even after heat
treatment for 24 h at 983 K. The mechanical properties of
the composites are only slightly affected by the annealing
time at 873 K, which is different from that for pure Al. In
view of the excellent mechanical properties and chemical
stability of the nanotubes, the engineering application of
nanotube9 for metal matrix composites could be ideal.
However, higher purification, of the nanotubes, more
homogeneous dispersion, and their alignment is still
necessary to produce an advanced composite reinforced
with nanotubes.
ACKNOWLEDGMENTS
The drawing and extrusion of the samples were,
respectively, carried out by Dr. T. Hasegawa and
Mr. H. Kobayashi and by Professor J. Kaneko and
Professor M. Sugamata. This work was partially
supported by The Mitsubishi Foundation. The authors
sincerely thank them.
J. Mater. Res., Vol. 13, No. 9, Sep 1998
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