Materials and Design 31 (2010) S96–S100

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Materials and Design

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

Spark plasma sintered multi-wall carbon nanotube reinforced aluminum

matrix composites
Jin-zhi Liao, Ming-Jen Tan, Idapalapati Sridhar *
School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: Aluminum (Al) matrix composites reinforced with 0–2.0 wt.% multi-wall carbon nanotubes (MWCNTs)
Received 19 July 2009 were prepared by thorough mixing of the composite powders in a roller mill and then sintered using a
Accepted 14 October 2009 spark plasma sintering (SPS) machine followed by hot extrusion. Fully dense Al–MWCNT composites
Available online 28 October 2009
were obtained. The microstructure and mechanical properties of these composites were characterized:
there is a significant enhancement in the Al–MWCNT composite properties at initial loadings 0.5 wt.%
Keywords: of MWCNTs when compared to Al samples without much increase in cost.
Aluminum
Ó 2009 Elsevier Ltd. All rights reserved.
Multi-wall carbon nanotubes (MWCNTs)
Spark plasma sintering (SPS)
Hot extrusion
Hardness
Tensile strength

1. Introduction
Since the discovery of carbon nanotubes (CNTs) by Iijima in
1991 [1], work carried out in recent years has revealed the intrigu-
ing mechanical, electrical and thermal properties of these novel
molecular scale wires [2–7]. Experimental measurements have
indicated that single-walled nanotubes (SWCNTs) have Young’s
moduli ranging from 1 to 5 TPa, and MWCNTs have an average va-
lue of 1.8 TPa [4]. Additionally, CNTs possess relatively low density,
varying from 1.2 g/cm3 for SWCNTs up to 1.8 g/cm3 for MWCNTs
[4]. The excellent mechanical properties combined with low den-
sity make CNTs an ideal reinforcing phase to design nanocompos-
ites with high specific strength and specific modulus. Many
researchers have endeavored to develop advanced CNT based com-
posites using metals, polymers and ceramic matrix phases, among
which Al has attracted intense interest as a metal matrix because
of its excellent strength, low density and corrosion resistance prop-
erties. The combination of unique properties of CNT and Al has
substantial potential in many weight sensitive applications such
as aerospace, defense etc., though still considerable research needs
to be done to identify optimal processing route. However, only a
few successful studies on CNT–reinforced Al matrix composites
have been reported [2–6,8,9], which are mainly attributed to the
processing difficulties and lack of understanding of the strengthen-
ing mechanisms. One of the key problems in manufacturing Al-CNT
composites is the clustering of CNTs in the Al matrix. This is due to
* Corresponding author. Tel.: +65 67904784.
E-mail address: msridhar@ntu.edu.sg (I. Sridhar).
the intricate entanglements of long and smooth CNTs and resulting
agglomeration due to strong van der Waals forces of attraction be-
tween them. Additionally, the weak interfacial bonding due to the
poor wettability of carbon with Al has been an obstacle to impart
effective load transfer between the CNT and the Al matrix. Further-
more, the formation of aluminum carbide (Al4C3) phase in the fab-
rication process complicates the strengthening mechanism of the
composite [3]. More recently, Kwon et al. [10] cliam in their Al–
CNT composites study that Al4C3 was formed and stabilized on
the surface of the tip of CNT and also helped in the transfer of stress
from Al matrix to the CNTs. But, their experimental study was re-
stricted to 0.5 vol.% of CNT. In view of the limited experimental
properties data on Al–CNT composites, the aim of the present
study is to fabricate Al–MWCNT composites using spark plasma
sintering followed by hot extrusion. The consolidated composites
are characterized for their microstructure and mechanical proper-
ties. The scope of the work is restricted to the MWCNT weight frac-
tion of 2.0%. MWCNTs were selected instead of SWCNT for cost
constraint.
2. Experimental details
The argon gas atomized Al powder (supplied by Henan Yuan
Yang Aluminum Industry Co., Ltd., China with purity 99.22%, aver-
age particle size of 5.0 lm) and MWCNTs (supplied by ShenZhen
Nano Technologies Port Co., Ltd., China with purity >95%, diameter
60–100 nm and length 5–15 lm) were used in this experimental
study. Sample micrographs of the Al powder and MWCNTs are

0261-3069/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2009.10.022
 J.-z. Liao et al. / Materials and Design 31 (2010) S96–S100
Fig. 1. Scanning electron micrographs (SEM) of (a) Al powder and (b) raw MWCNTs.
shown in Fig. 1. The MWCNTs were purified by 65% concentrated
nitric acid and ultrasonicated for 6 h. The suspension was later fil-
tered and neutralized with sodium hydroxide pellets in the ratio of
1 pellet to 100 ml of distilled water. The MWCNTs were then sub-
jected to repeat rinsing by distilled water until a pH value of 7 was
obtained. The suspension was then filtered and baked dry at 110 °C
for 2 h to remove any residues. MWCNTs were then treated with
sodium dodecyl sulfate (SDS) surfactant in order to decrease the
van der Waals force between them [11,12] to facilitate their ease
of dispersion: SDS, an anionic surfactant adsorbs onto the surface
of the nanotubes bundles according to the phase diagram of the
NaDDS–SWNT–water system [12]. The mixture was then ultraso-
nicated for 4 h and baked dry at 110 °C for 2 h to remove any res-
idues. This cleaning procedure resulted in the decreased D-band
intensity in the Raman spectrum.
Measured amounts of MWCNTs (to achieve a weight fraction of
0.5%, 1.0% and 2.0%) were then mixed with Al powder in a plastic
jar and the mixtures were blended by can rolling. For the purpose
of comparison pure Al sample was also fabricated. The Al powder
and MWCNT mixture was cold compacted and subsequently sin-
tered using ‘‘Dr. Sinter SPS-1050” machine at a temperature of
500 °C with holding time of 20 min under high vacuum (10 Pa).
Natural cooling was applied. Subsequently, the sintered cylindrical
samples of 30 mm diameter and 22 mm length were hot extruded
into a cylindrical rod of 10 mm diameter at 500 °C giving an extru-
sion ratio of 9:1. The extrusion process was carried out at 5 mm/s.
In order to investigate the effect of MWCNTs content on the
strength and ductility of the composite, uniaxial tensile, compres-
sive and hardness tests were carried out by machining the test
samples from the as-sintered and as-extruded rods. For tensile
tests, a dog-bone type of cylindrical sample with a diameter of
5 mm and gauge length of 28 mm was used. The tensile test was
carried out under displacement control at a strain rate of
Fig. 2. SEM micrographs of the mixed Al and MWCNTs powders (a) Al–0.5 wt.% MWCNT and (b) Al–2.0 wt.% MWCNT.
S97
103 s1. For compression tests, cylindrical rods of 6 mm diameter
and 9 mm length were machined and tested at a strain rate of
104 s1. A laser extensometer was used for the accurate measure-
ment of strains. Optical microscopy, scanning and transmission
electron microscopy (SEM, TEM) were used to characterize the
microstructure of the samples. Hardness measurements were done
using a Vickers microindenter.
3. Results and discussion
It is known that the mixing process and its duration determine
the effective dispersion of MWCNTs in the Al powder. SEM micro-
graphs of the blended Al–MWCNT powders are depicted in Fig. 2.
There seems to be homogeneous mixing of Al powder and
MWCNTs at 0.5 wt.% loading and there is considerable agglomera-
tion of MWCNTs at 1.0 wt.% and 2.0 wt.%.
Fig. 3a–c shows the microstructure of the as-sintered pure Al
and Al–MWCNT composites with 0.5 wt.% and 2.0 wt.% reinforce-
ment phase at the same magnification. Equiaxial grains were ob-
served in the pure Al and its composites. The densification of the
as-sintered samples is not complete as pores existed in the samples
(density reached around 95%). Also, there seems to be a few Al
spherical particles without considerable mass diffusion around
them. Composites that contained MWCNTs have a dark outline
along the grain boundaries. This indicates that the MWCNTs are
distributed homogenously along the grain boundaries. All the sin-
tered samples show approximately the same grain size. The micro-
structure of the as-extruded pure Al and Al–MWCNT composites
with 0.5 wt.% and 2.0 wt.% loadings are as shown in Fig. 3d–f.
The original spherical grains of the as-sintered samples were elon-
gated along the extruded direction after extrusion, with an average
grain size of 6.5 lm. In addition, voids remaining in the sintered
S98 J.-z. Liao et al. / Materials and Design 31 (2010) S96–S100

samples are pinched off due to the severe plastic deformation in 50

hot extrusion process. The relative density of all the extruded sam-
45
ples was above 99.0%. By comparing the microstructure of the pure
Al metal and composites, no change in the microstructure was ob- 40

HV hardness (kg/mm )
2
served from the optical micrographs. From above, it seems that 35
MWCNTs in the grain boundary play a pinning effect of MWCNTs
30
to restrain the grain growth. However, when larger amount of
MWCNTs were added to the aluminum powder, the MWCNTs tend 25
to more easily conglomerate and impeded the densification pro- 20
cess, as pores are more apparent and larger with the increasing
15
content of MWCNTs (Fig. 3b and c). The X-ray diffraction spectrum
(not shown here) of the as-sintered and as-extruded Al and Al– 10
MWCNT composites did not reveal the presence of either alumina 5
or aluminum carbide. Also, any presence of alumina layer on the Al
0
particles get destroyed by the surface cleaning effect of the SPS [2]. -0.5 0.0 0.5 1.0 1.5 2.0 2.5
But it is noted that the absence of aluminum carbide may be due to CNTs contents (wt.%)
the low content of it or limited resolution of the XRD.
Fig. 4 shows the uniaxial compressive and tensile stress–strain Fig. 5. Variation of Vickers micro-hardness with MWCNT loadings in Al matrix
composites. The hardness measurements on the pure Al sample are also included.
response of the as-extruded samples, respectively. For both com-
pressive and tensile tests, the strength reached maximum when
the 0.5 wt.% MWCNTs was added, but decreased with increasing
amount of MWCNTs (1.0 and 2.0 wt.% MWCNTs). The as-extruded ing a fracture strain of 35% in tension (see Fig. 4b). The tensile sam-
Al and Al–MWCNT composites showed excellent ductility: show- ples failed by necking. In contrast, Sridhar and Karthic [13] have

Fig. 3. Microstructure of the as-sintered (a) pure Al, (b) Al–0.5 wt.% MWCNT, (c) Al–2.0 wt.% MWCNT composite; and as-extruded (d) pure Al, (e) Al–0.5 wt.% MWCNT and (f)
Al–2.0 wt.% MWCNT composite (arrow indicates the extrusion direction).

120 200
Al-0.5CNTs
100 Al-0.5CNTs
Comressive stress (MPa)

Al-2.0CNTs
160
Tensile stress (MPa)

Al-1.0CNTs
Pure Al
80
120
Al-2.0CNTs Al-1.0CNTs pure Al
60
80
40

40
20
(a) (b)
0 0
0.0 0.5 1.0 1.5 2.0 0 5 10 15 20 25 30 35 40
Compressive strain (%) Tensile strain (%)

Fig. 4. (a) Uniaxial compressive stress–strain and (b) uniaxial tensile stress–strain response of extruded samples.
 J.-z. Liao et al. / Materials and Design 31 (2010) S96–S100
Table 1
Mechanical properties with cost of the pure Al and Al–MWCNT composites (only take into account the cost of the raw materials).
Materials Yield strength at 0.2% offset UTS (stress at 1.2% compressive strain)
(MPa) (MPa)
Pure Al +66 80 +153
Al–0.5 wt.% MWCNT +96 94 +174
Al–1.0 wt.% MWCNT +78 79 +154
Al–2.0 wt.% MWCNT +88 86 +160
Note: Positive (+): tensile samples; negative (): compressive samples.
synthesized Al–MWCNT composites by furnace sintering at 580 °C
and followed by cold extrusion. Their limited experimental study
indicated improvement in mechanical response over the MWCNTs
loading range (up to 2.0 wt.%) with limited ductility. Vickers hard-
ness ranging from 45–50 kg/mm2 was measured for the as-ex-
truded pure Al and Al–MWCNT composites, as shown in Fig. 5. In
general, the hardness increases with the content of MWCNTs.
Hardness reached maximum for the 0.5 wt.% MWCNT/Al, but then
dropped with the further loading of MWCNTs. Similar observation
was also made by Deng et al. [8] in their Al–MWCNT composites
study.
Table 1 summarizes the mechanical properties of pure Al and
Al–MWCNTs composites along with their estimated costs (only
take into account the cost of the raw materials). It can be seen that
the mechanical properties of the Al–MWCNT composites reach
maximum when MWCNTs weight percentage was 0.5%, while at
1.0% and 2.0% loadings the measured strength and hardness values
are slightly higher than that of Al within experimental scatter. The
increase in raw material cost of the composite is not so significant
even though SPS based sintering is quite expensive in view of
machinery.
Herein, we explored Kelly–Tyson equation [14] in predicting the
MWCNT based composites strength, but found the experimentally
measured strength values to be much lower than the predicted
upper bound ones (the difference up to 70%). George et al. [4] have
detailed that coefficient of thermal expansion mismatch between
the CNTs and the Al matrix, Orowan looping and shear-lag theory
as three strengthening mechanisms for CNT based metal matrix
composites. These will be explored in our future work after rectify-
ing the problems with CNTs agglomeration. The experimental mea-
sured strength values are much lower that the predicted ones. It is
suggested this can be due to several factors: Firstly, the clustering
Fig. 6. TEM image of the extruded Al–0.5 wt.% MWCNT composite showing
alignment of MWCNTs along the extrusion direction.
S99
Vickers hardness (HV) Cost of the samples for 100 g (USD)
98 45 40.0
125 50 40.3 (" 0.75%)
106 47 40.6 (" 1.50%)
102 48 41.2 (" 3.00%)
of the MWCNTs. The clustering of MWCNTs in the Al matrix was
supported by SEM and TEM. Clusters of MWCNTs were found in
the mixed composite powders at 2.0 wt.% MWCNTs (Fig. 2). Also
from the TEM micrograph of the extruded Al–MWCNT samples
(see Fig. 6), MWCNT clusters along the extruded direction were vis-
ible. The clustering of high percentage of MWCNTs in Al matrix
was also reported by several researchers [8,9,15]. In addition, the
agglomerated MWCNTs not only failed to transfer or share the
stress effectively, but also became fracture initiation sources. Final-
ly, there may be insufficient interfacial bonding between the
MWCNTs and the Al matrix, which indicates that chemically func-
tionalized MWCNTs should be considered for composites fabrica-
tion. From the obvious necking characteristic of the tensile
curves of the Al–MWCNT composites (similar to that of the pure
Al, see Fig. 4b), it is suggested that MWCNTs were pulled out of
the matrix (otherwise the stress–strain curve show abrupt drop
in load due to the fracture of MWCNTs), and this may due to the
insufficient adhesion between MWCNTs and Al matrix.
4. Conclusions
1. Al–MWCNT composites were successfully fabricated by spark
plasma sintering followed by hot extrusion to near full density.
2. The SDS treated MWCNTs and roller milling of the Al powder
and MWCNTs has effectiveness in dispersing the MWCNTs for
low weight fraction and is not effective at higher weight
fractions.
3. The reinforcement phase i.e. MWCNTs are aligned along the
extrusion direction and predominantly located at the grain
boundaries.
4. The mechanical properties of the Al–0.5 wt.% MWCNT compos-
ites are enhanced noticeably at room temperature, and decrease
with increasing the content of MWCNTs due to the agglomera-
tion of MWCNTs and insufficient interfacial bonding.
Based on the above experimental observations we explore using
chemically functionalized MWCNTs for consolidating composites
in our future work and study strengthening mechanism in relation
to the applied manufacturing route.
Acknowledgements
Authors thank Prof. Michael Khor Khiam Aik for allowing the
authors’ to use the Dr. Sinter SPS Machine. IS thanks the financial
support from NTU Academic Research Fund (AcRF) via project
number 19/06.
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