Wear 255 (2003) 677–681

Tribological properties of hot-pressed alumina–CNT composites

J.-W. An a,b , D.-H. You a,b , D.-S. Lim a,b,∗
a Division of Materials Science and Engineering, Korea University, 1 Anam-dong 5ka, Sungbuk-ku, Seoul 136-701, South Korea
b Ceramic Processing Research Center, Hanyang University, Seoul 133-791, South Korea

Abstract
Carbon nanotubes (CNTs) have lately attracted remarkable attention as reinforcements of materials because of their exceptional me-
chanical and electronic properties. However, studies on the ceramic–CNT composite have been rarely reported. Alumina–CNT composites
have been produced to investigate the effect of carbon nanotube addition on the mechanical and tribological properties by hot-pressing.
The alumina–CNT composite powder was prepared by catalytic pyrolysis of acetylene gas with an iron nitrate impregnated alumina.
The contents of iron nitrate were controlled from 0 to 0.5 mol.% to change the CNT compositions in the alumina–CNT composite. The
microstructures and mechanical properties of hot-pressed composites have been investigated to explain the effect of the CNT compositions
on the tribological properties of the alumina reinforced with CNT composites.
© 2003 Elsevier Science B.V. All rights reserved.
Keywords: Carbon nanotube (CNT); Alumina–CNT composite; Tribological property

1. Introduction provide essential informations for tribological applications.

It is well known that ceramic whiskers can improve the
fracture resistance of the ceramic composites [1–3]. Recent
studies of SiC whisker reinforced alumina and silicon nitride
reveal that there are substantial improvements in tough-
ness and wear resistance [4,5]. Furthermore, carbon nan-
otubes (CNTs) have recently been considered as reinforcing
elements in ceramic matrix composites due to their unique
mechanical properties [6,7]. Tensile strength and Young’
s modulus of CNT have been measured to be as high as
200 GPa and 1 TPa, respectively, which are much higher
than that of whiskers [8]. Siegel et al. reported that fracture
toughness of 10 vol.% CNT added alumina composites was
increased up to 24% compared to monolithic alumina [9].
Controversial results with CNT added alumina composites
also have been reported. Laurent et al. showed that rein-
forcing effect that was expected from the addition of CNTs
bundles was not observed for CNTs–Fe–Al2 O3 composites
[10]. The fracture toughness values of CNT added alumina
composites were lower than or similar to that of Fe–Al2 O3
composites. However, their SEM observation indicated that
nanotube bundles could dissipate some fracture energy. Re-
ported studies seems to recommend additional studies.
In this study, the effect of CNT addition on tribologi-
cal behavior of alumina composites has been examined to
∗ Corresponding author. Tel.: +82-2-3290-3272; fax: +82-2-929-5344.
E-mail address: dslim@korea.ac.kr (D.-S. Lim).
The role of alumina–CNT debris and micro-hardness of the
composites on the frictional coefficient and wear rate have
been also investigated.
2. Experimental procedure
Alumina–CNT composite powders were synthesized in
the catalytic decomposition of acetylene over alumina pow-
ders impregnated with iron catalysts. Appropriate amount
of three materials indicated in Table 1 (alumina, MgO,
Fe(NO3 )3 ·9H2 O) were mixed by planetary ball milling for
12 h to prepare the alumina powder impregnated with iron
catalysts. The powder was mixed in ethanol by alumina
balls (10 mm in diameter). After ball milling, the ethanol
solution was removed via rotary evaporation at 80 ◦ C. The
materials were then heated at 150 ◦ C overnight followed by
grinding into a fine powder.
For the CNT synthesis, each alumina powder having four
different iron catalyst contents (Fe01, Fe05, Fe10 and Fe50)
was placed in an alumina boat mounted in a tube furnace.
Details of the experimental set-up are described elsewhere
[11]. The production of CNTs was carried out at 750 ◦ C
with 2 h reaction time under 20:100:400 sccm C2 H2 :H2 :N2
gas flow.
After the synthesis, the composite powders were exam-
ined by a SEM (S-4300, Hitachi, Japan) to measure the
length, diameter and uniformity. Samples were dispersed

0043-1648/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0043-1648(03)00216-3
678 J.-W. An et al. / Wear 255 (2003) 677–681

Table 1 load cell was recorded throughout the tests. The load cell
Starting materials compositions of samples produced an electrical output depending on the frictional
Component Sample (mol.%) force. The electrical signal amplified by a multimeter was
A Fe01 Fe05 Fe10 Fe50
stored in a computer via a general purpose interface bus
(GPIB). The amount of wear was obtained by measuring
Al2 O3 a 98.75 98.65 98.25 97.75 93.75 the weight loss with a microbalance. After the wear tests,
MgOb 1.25 1.25 1.25 1.25 1.25
Fe(NO3 )3 ·9H2 Oc – 0.10 0.50 1.00 5.00
the worn surfaces of each sample and wear debris were
examined by the SEM.
a AKP-30, Sumitomo Chemical, Osaka, Japan.
b EP, Junsei Chemical, Tokyo, Japan.
c Fluka Chemie GmbH, Buchs, Switzerland.
3. Results and discussion

in a carbon tetrachloride (CCl4 ) solution, and then scooped Fig. 2 shows micrographs of the prepared alumina pow-
up onto a holey carbon microgrid. For TEM observa- ders and CNT materials. CNTs have a diameter of about
tions, these specimens were examined with a side-entry 10–50 nm, while their length is about 5–10 ␮m. The diame-
type HRTEM (H9000-NAR, Hitachi, Japan) operating at ter and the length of CNTs tended to increase with increas-
300 kV with a point resolution of 0.18 nm. HRTEM was ing the iron catalyst contents. Fig. 3 shows a typical TEM
used to determine the wall structure of individual car- micrograph of the CNT. It clearly shows that the nanotube
bon nanotubes. The weight percentage of the carbon in is a multi-walled hollow tube, not solid fiber. The fringes
the composite powder was obtained by an elemental ana- on each side of the tube represent individual cylindrical
lyzer (Flash EA 1112 series, CE Instruments, Italy). The graphitic layers. The CNT has approximately 15–20 walls
difference between the specific surface area of the com- of graphitized carbon.
posite powder and that of the same powder after oxidation The carbon content and the difference between the spe-
in air at 850 ◦ C (carbon-free powder) was measured by cific surface area (S) of composite powder and that of
the BET (Branauer–Emmett–Teller) method (ASAP 2010, carbon-free powder were shown in Fig. 4. The carbon con-
Micromeritics, USA). tent and S are sharply increased as increasing the iron cat-
The synthesized alumina–CNT composite powders were alyst content up to 1 mol.%. In the range of 1–5 mol.% iron
hot-pressed in a graphite die in argon atmosphere at a tem- catalyst contents, the carbon content and S are gradually
perature of 1800 ◦ C under a pressure of 40 MPa for 1 h.
Hardness was measured by using a Vickers microhardness
tester under a load of 2 N for 10 s. The fractured surfaces of
hot-pressed specimens were examined by the SEM.
The friction and wear experiments were performed by
using a ball-on-reciprocating flat geometry. Fig. 1 shows a
schematic diagram of the wear tester. The silicon nitride
ball (NDB100, Norton, USA) of 6.35 mm in diameter was
used against flat alumina–CNT composite sample surfaces
which were polished with 1 ␮m diamond slurry. The normal
load and sliding speed were fixed at 25 N and 10 mm/s,
respectively. The reciprocating stroke was 10 mm and the
test duration was 2 h. The frictional force transferred to a

Fig. 2. The SEM micrographs of prepared alumina powders and CNT

Fig. 1. Schematic diagram of the wear tester. materials: (a) at a low magnification and (b) at a high magnification.
 J.-W. An et al. / Wear 255 (2003) 677–681 679

Fig. 3. Typical TEM micrograph of the CNT synthesized in the catalytic

decomposition of acetylene over alumina powders impregnated with iron
catalysts.

increased. It shows that the increase in the amount of iron

catalyst lead to the increase in the amount of CNTs. Peigney
et al. suggested that S is related to the quantity of nanotube
in the composite powders [7,12].
Fig. 5 shows the fractured surface morphologies of
the hot-pressed samples of Fe01 (2.7 wt.% CNT), Fe05
(4.1 wt.% CNT) and Fe50 (12.5 wt.% CNT). The grain
size of alumina tends to decrease as the CNT content is
increased. The CNTs were located in grain boundaries
of alumina. The cohesion between the CNTs and alu-
mina grains appears to be poorer as the CNT content is
increased.
A maximum microhardness is observed near 4% of CNT
content (Fig. 6). Hardness shows an increase with increasing
CNT content up to 4% CNT content. Hah et al. reported that
the hardness of alumina is proportional to (grain size)−1/2
[13]. The microhardness is expected to increase as the CNT
content is increased if we only consider the grain size ef-
fect. In addition to the grain size effect, the reinforcement

Fig. 5. The fractured surface morphologies of the hot-pressed alumina

composites: (a) with 2.7 wt.% CNT content, (b) with 4.1 wt.% CNT
content, and (c) with 12.5 wt.% CNT content.

role of CNTs in alumina composite might also affect the

Fig. 4. The carbon content and the difference between the specific surface
area (S) of composite powder and that of carbon-free powder as a
function of iron catalyst content.
increase in hardness. Further addition of CNTs lowers the
microhardness significantly. This phenomenon is probably
due to the difficulty in dispersing CNTs homogeneously in
the composite and the problem of the poor cohesion be-
tween CNTs and the matrix as suggested by Laurent et al.
[10].
The variations of wear loss and friction coefficient as a
function of CNT content are shown in Fig. 7. Weight loss
of the hot-pressed composite having about 4% CNT (sam-
ple Fe05) is decreased by nearly 45% as compared to that
of the hot-pressed specimen having 0% CNT (sample A).
680 J.-W. An et al. / Wear 255 (2003) 677–681

Fig. 6. The variations of microhardness as a function of CNT content.

This enhancement of tribological property also related to

the grain size effect and the reinforcement effect of CNTs
addressed in the microhardness data. Wear losses were sig-
nificantly increased as the CNT content is above 10%. This
phenomenon could be also explained by the deterioration
of the mechanical properties due to previously described
difficulties in dispersing CNTs and poor cohesion. Figs. 6
and 7 suggested that the addition of CNTs up to 4% has a
positive influence on the reinforcement effect but a nega-
tive influence on the densification at a higher CNT content
(over 10%). SEM micrographs of damaged surface (Fig. 8)
after the wear tests confirm that the described above. The
0.5% CNT content specimen (Fig. 8b) has smaller and
less wear debris as compared to 0% (Fig. 8a) and 12.5%
CNT content specimen (Fig. 8c). The densification prob-
lems can be related to the generation of larger size and
greater volume of debris in 12.5% CNT content specimen.
The study about the finding of the solution of densification
problems could extend the potentialities of the CNTs in the
composites. Fig. 8. The SEM micrographs of damaged surface after the wear tests
of alumina composite: (a) with 0 wt.% CNT content, (b) with 4.1 wt.%
CNT content, and (c) with 12.5 wt.% CNT content.

Fig. 7 also shows that the friction coefficient decreased

Fig. 7. The variations of wear loss and friction coefficient as a function
of CNT content.
gradually as the CNT content increased from 0 to 10%. The
friction coefficient drops sharply at 12.5% of CNT content.
Fig. 9a shows the damaged surface morphology of 12.5%
CNT specimen after the wear test. It is seen that the wear
debris consisted of the mixture of CNTs and alumina parti-
cles. We also found that the CNTs in the wear debris, which
was collected around the wear track, maintain their shape
even after the wear tests (Fig. 9b). The decrease in friction
coefficient is due to the lubricating properties of the CNTs
(graphite). Furthermore, the rolling motion of CNTs at the
interface between the specimen and the ball can probably
lower the friction coefficient.
 J.-W. An et al. / Wear 255 (2003) 677–681
Fig. 9. (a) The damaged surface morphology and (b) the wear debris
morphology, collected around the wear track, of 12.5 wt.% CNT content
alumina composite after wear test.
4. Conclusions
Alumina–CNT composites with the CNT contents rang-
ing from 0 to 12.5 wt.% were fabricated to investigate the ef-
fect of CNT addition on wear resistance. The alumina–CNT
composites were obtained by hot-pressing the alumina–CNT
composite powders which were synthesized in the catalytic
decomposition of acetylene over alumina powders impreg-
nated with iron catalysts. The enhanced wear and mechani-
cal properties in the range of 0–4% CNT content are a result
of the CNT’s behavior in reinforcing filler in alumina com-
posite and the grain size effect. But, if the CNT content is
over 10%, the mechanical properties are decreased, because
of the poor cohesion between the CNT and the matrix. The
decrease in friction coefficient with increasing CNT con-
tent is due to the lubricating properties of the CNTs and the
681
rolling motion of CNTs at the interface between the surface
of specimen and the counterparts.
Acknowledgements
This work was supported by the Ceramic Processing Re-
search Center (CPRC) through a grant of the Korea Science
and Engineering Foundation.
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