Composites Science and Technology 71 (2011) 705–709

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Composites Science and Technology

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

Interfacial analysis between Mg matrix and carbon nanotubes in Mg–6 wt.% Al

alloy matrix composites reinforced with carbon nanotubes
Hiroyuki Fukuda a,⇑, Katsuyoshi Kondoh b, Junko Umeda b, Bunshi Fugetsu c
a
Graduate School of Engineering, Osaka University, 1 Yamadaoka, Suita, Osaka 565-0871, Japan
b
Joining and Welding Research Institution, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan
c
Hokkaido University, 5 Niow, Kita-ku, Sapporo, Hokkaido 060-0810, Japan

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

Article history: Magnesium containing 6 wt.% aluminum alloy composites reinforced with carbon nanotubes were fabri-
Received 12 November 2010 cated with powder metallurgy based wet-processing. Yield stress and tensile strength were successfully
Received in revised form 11 January 2011 improved by the addition of carbon nanotubes. Field emission-transmission electron microscopy micro-
Accepted 20 January 2011
structural analysis clarified that needle-like ternary carbides of Al2MgC2 were synthesized at some inter-
Available online 25 January 2011
faces between magnesium matrix and carbon nanotubes, and the other interfaces were clean without any
other materials or defects. Tensile loading transfer from magnesium matrix to carbon nanotubes was
Keywords:
effectively strengthened by both the production of Al2MgC2 compounds and the clean interface between
A. Carbon nanotubes
A. Metal-matrix composites (MMCs)
magnesium matrix and carbon nanotubes.
B. Mechanical properties Ó 2011 Elsevier Ltd. All rights reserved.
D. Transmission electron microscopy (TEM)
E. Powder processing

1. Introduction route in solid-state [2–4,6]. Authors in the present study invented

the wet-processing using water based zwitterionic surfactant solu-
Carbon nanotubes (CNTs) having peculiar cylindrical shape of tion dispersed with un-bundled CNTs [10], and reported the
nano-order diameter and micro-order length are promising mate- improvement of yield stress and tensile strength compared to that
rials in many fields. Since they show excellent mechanical proper- of pristine materials [2,6]. With titanium (Ti) matrix, the compos-
ties and flexible electrical and thermal conductivity, CNTs have ites showed significantly higher strength than the monolithic
been expected as one of next generation materials since their dis- material with maintaining elongation of 10–15% or more [6]. How-
covery in 1991 [1]. The research using CNTs as reinforcements in ever, with pure Mg and AZ31 Mg alloy matrix, the composites lost
metal-matrix composites (MMCs) is one of those examples as in much ductility instead of improving strength compared to mono-
the previous works [2–6]. However, the agglomeration of CNTs, lithic material. This was because of the incorporation of thick
due to their strong van der Waals forces between utmost surface layers of magnesium oxide (MgO) during sample fabrication pro-
carbon atoms, prevents their uniform dispersion as un-bundled cess. While using MgO to strengthen the interface was quite useful
CNTs in MMCs. CNT fragmentation [7,8] and surface functionaliza- for Mg whose binary carbides were unstable at atmospheric condi-
tion [9] have been usually applied as effective procedures because tion [11], this idea caused much reduction of ductility. On the other
these processes possess powerful ability to disassemble CNT bun- hand, a few reports discovered a formation of ternary carbides of
dles. However, since they also induce severe damages and degrade Al2MgC2 in Mg alloy matrix containing fraction of Al element such
CNT strength, these processes are hardly accepted when CNTs are as AZ31, AZ61, and AZ91 with various carbon materials [12–17].
incorporated into MMCs as reinforcements. In addition, with con- According to their observations, needle or plate-like Al2MgC2 dis-
ventional casting procedures, CNTs easily experience floatation continuously grew into the matrix. Such protrusions might effec-
due to extremely low density of CNTs, 1.4 g/cm3, compared to that tively improve the interfacial strength between Mg matrix and
of metals such as 1.74 g/cm3 for Mg, 2.7 g/cm3 for aluminum (Al), CNTs. Therefore, AZ61 Mg alloy composites reinforced with un-
and 7.87 g/cm3 for iron (Fe). Thus, fabrication of MMCs reinforced bundled CNTs were fabricated under the condition which facili-
with CNTs was mainly conducted with powder metallurgy based tates Al2MgC2 production in the present study. The fabricated com-
posites were evaluated with tensile testing at ambient
⇑ Corresponding author. Fax: +81 06 68798669.
temperature and analyzed with field emission-scanning electron
E-mail address: [email protected] (H. Fukuda).
microscopy (FE-SEM), X-ray diffractometer (XRD) and field emis-

0266-3538/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2011.01.015
706 H. Fukuda et al. / Composites Science and Technology 71 (2011) 705–709

(a) ( b)

Fig. 1. FE-SEM observation on as-received AZ61 Mg alloy powders (a) and CNTs (b).

sion-transmission electron microscopy (FE-TEM). Tensile strength

of the composites was improved compared to that of monolithic
AZ61 Mg alloy. Besides, FE-TEM microstructural analysis clarified
the presence of needle-like Al2MgC2 compounds between Mg ma-
trix and CNTs.

2. Experimental procedure

In the present study AZ61 Mg alloy powders, shown in Fig. 1a,

having chemical compositions of Al, 6.38; Zn, 0.68; Mn, 0.28; Si,
0.04 in wt.% were prepared as a raw powder. Multi-walled carbon
nanotubes commercially named VGCF, which was the product of
SHOWA DENKO Co. Ltd. shown in Fig. 1b, were also used as a rein-
forcement raw material. According to its data sheet, the mean
diameter and length were 150 nm and 8 lm, respectively. Fig. 2a
and b exhibited FE-TEM (JEOL, JEM-2100F) observation on surface
Fig. 3. Nominal tensile behavior of the fabricated composites (a) is AZ61 pristine
of an as-received CNT. Black arrows in (a) indicate amorphous area
material; (b–d) are AZ61 with 1.56, 1.37 and 0.71 vol.% CNTs, respectively.
on the CNT surface. The thickness of this area was at most 2–3 nm
as shown in (b). In addition, while CNT catalysts were usually re-
mained, no such particles were present at the top of CNTs. Besides,
nothing remained after burning of CNTs in air atmosphere. There- content measured by the infrared-absorption technique. For con-
fore, as-received CNTs were entirely clean with few disordered car- venience, the composites are coded depending on the CNT content;
bons or other contaminations. (a), (b), (c), and (d) are pristine AZ61, AZ61 with 1.56, 1.37, and
While the above wet-process [2,6] was also employed in the 0.71 vol.% CNTs, respectively.
fabrication process, instead of water base one, isopropyl alcohol The specimens were evaluated with tensile test at room tem-
(IPA) base zwitterionic surfactant solution was used in the present perature under strain ratio of 5.0  10 4/s. For the test, the ob-
study to decrease brittle MgO productions as low as possible by tained composites were machined into rod type specimens
preventing direct contact of water with AZ61 powders. The com- having 15 mm in gauge length and 3 mm in diameter. XRD (Shima-
posite fabrication condition was almost same as previous research dzu, XRD-6100) and FE-TEM were operated to identify the pres-
[2] except the sintering time of 5.5 h for promotion of Al2MgC2 for- ence of Al2MgC2 compounds in the composites. Also, fractured
mation. Since no other carbon sources were included in the com- surface of the specimens were observed with FE-SEM (JEOL, JSM-
posites, CNT content of each composite was regarded as C 6500F) to understand fracture behavior of CNTs.

(a) (b)

10 nm 10 nm

Fig. 2. FE-TEM photos of surface of an as-received CNT (a) is a tip and (b) is a side surface of a CNT. Black arrows indicate amorphous area on the CNT surface. The thickness of
this area was less than 2–3 nm or not present as shown in (b). CNT was entirely clean with few disordered areas or other contaminations.
 H. Fukuda et al. / Composites Science and Technology 71 (2011) 705–709 707

addition of CNTs. With 0.71, 1.37, and 1.56 vol.% CNTs, yield stress
Mg increased 21.1, 23.4, and 28.5 MPa compared to that of pristine
Al11Mn4
Al12Mg17
AZ61, respectively. Additionally, with 0.71, 1.37, and 1.56 vol.%
MgO CNTs, the elongation was 12.2%, 8.3%, and 5.4% compared to
14.7% of pristine AZ61 in this study, respectively although that of
pure Mg and AZ31 Mg alloy composite reinforced with 1.14 and
1.43 vol.% CNTs were less than 3% and 4% in the previous study
(a) [2], respectively.

(b) Al 2 MgC 2 3.2. Identification of interfacial Al2MgC2

(c)
XRD profiles of all samples were exhibited in Fig. 4. Peaks of Mg
(d) matrix, MgO, and intermetallic compounds of Al11Mn4 and
Al12Mg17 were identified in all profiles. No significant differences
in peak shifts or peak intensities were observed in these results.
Since its peak intensities were almost same regardless of samples
with or without CNTs, it could be recognized that the identified
MgO originated from the surface oxide film of the as-received
AZ61 raw powders. Brittle MgO formation in the composite was re-
Fig. 4. XRD profiles on AZ61 with and without CNTs (a) is AZ61 pristine material;
(b–d) are AZ61 with 1.56, 1.37 and 0.71 vol.% CNTs, respectively. Except (a), a peak duced by using IPA base solution in the fabrication step. Thus, the
for Al2MgC2 was identified at the angle range of 2h = 54–55°. composites could maintain relatively high ductility as shown in
Fig. 3. In contrast, a peak between h = 54° and 55° was observed
only in samples with CNTs. Several reports clarified the ternary
3. Results and discussion carbides of Al2MgC2 in Mg–Al alloys containing various carbon
sources as above described [12–17]. One of these articles distin-
3.1. Tensile behavior of AZ61 Mg alloy composites reinforced with guished two types of Al2MgC2 of T1 and T2 [12]. According to X-
CNTs ray diffraction data of Al2MgC2 – T2 indexed in the reference, the
lattice spacing for the third peak of Al2MgC2 – T2 was 1.6887 Å. This
The tensile curves were presented in Fig. 3. Yield stress and ulti- can be calculated into 2h = 54.35°, which was in the range of the
mate tensile strength of AZ61 Mg alloy were enhanced by the unknown peak identified in AZ61 composites reinforced with

Fig. 5. Al2MgC2 at the interface between Mg matrix and CNTs (a) is a bright field photo and (b) is a selected area diffraction pattern of areas around (a). Materials
corresponding to each diffraction ring were summarized in (c). Al2MgC2 pointed with a white arrow protruded from CNT surface into Mg matrix.
708 H. Fukuda et al. / Composites Science and Technology 71 (2011) 705–709

(a)
(a) (b)

200 nm

Fig. 6. Fractured CNTs on the fractured surface of AZ61 with 1.37 vol.% CNTs (a and b). CNTs were peeled out from their outer graphene sheets as clearly shown with white
arrows in (b).

Fig. 5 might promote the interfacial strength between Mg matrix

and CNTs. On the other hand, no other materials or defects were at
the interface where no Al2MgC2 was synthesized as shown in
Fig. 7; the interface was quite clean. Goh et al. reported the improve-
ment of tensile properties of pure Mg by CNT incorporation [5].
Since, in their process, MgO could be scarcely produced at the inter-
face, this means that even the interface without any materials could
provide interfacial strength more or less enough to transfer tensile
loading. Hence, the tensile improvement obtained in the present
study was due to both the production of Al2MgC2 and the clean inter-
face between Mg matrix and CNTs.
Moreover, Pei et al. reported degradation of carbon fibers de-
rived from much production of Al2MgC2 on their surface [13]. In
their case, Al2MgC2 strengthened the interface between Mg matrix
and the fibers, but at the same time, weakened mechanical proper-
ties of fibers by inducing sharp notch on the fiber surface. However,
Fig. 7. Clean interface between Mg matrix and CNTs. No materials were observed in the present study, no precipitates were observed on the frac-
around the interface. tured areas of CNTs as shown in Fig. 6. That is, the nanotubes were
not fractured where Al2MgC2 was synthesized. Besides, with TEM
observation, lots of CNTs having clean surface without any materi-
CNTs. Here, the first, 34.35°, and second, 43.93°, peaks of Al2MgC2 –
als as well as those having Al2MgC2 protrusion were observed as
T2 were hardly identified due to the larger peaks at very near to the
explained above. Hence, Al2MgC2 production in this study was less
diffraction angle of Mg matrix and Al12Mg17, respectively. Besides,
to degrade the strength of CNTs like the reference [13]; this is
the peak intensity of the unknown peak increased proportionally
probably related to the difference in graphitization of fibers used
to CNT content as shown in Fig. 4. This point also justified that ori-
in each study. CNTs could provide nearly maximum tensile perfor-
gin of the unknown peak was related to the nanotubes. A TEM
mances to Mg matrix since the Al2MgC2 production in the compos-
photo at the interface between CNT and Mg matrix was presented
ites insignificantly influenced on reducing CNT strength.
in Fig. 5. As pointed with a white arrow, Fig. 5a showed that a nee-
dle-like phase obviously different from Mg matrix projected from
not all but some CNT surfaces. The selected area diffraction pattern 4. Conclusion
around Fig. 5a shown in Fig. 5b revealed the presence of Al2MgC2
inside the area. Further, in some of reported articles [13,14,17], Yield stress and tensile strength of AZ61 composite reinforced
Al2MgC2 was identified as needle-like protrusions directly ex- with CNTs were improved compared to pristine AZ61. Elongation
tended from carbon fibers. The shape of Al2MgC2 in these refer- decrease was relatively reduced compared to that previously re-
ences was similar to that produced in the present study. ported. In the present study, the synthesis of excess brittle MgO
Therefore, the unknown needle-like phase could be recognized as was prevented by using IPA base solution instead of water base
Al2MgC2. Although a CNT in this photo was shown as an ellipsoid one. XRD and TEM analysis clarified the formation of Al2MgC2 pro-
not a disk, this is because longitude axis of CNT relatively inclined trusions at some interfaces between Mg matrix and CNTs. Besides,
from the normal axis of TEM sample surface. the other interfaces showed clean without any other materials or
defects. Therefore, mechanical strength of the composites in-
creased due to both the production of Al2MgC2 and the clean inter-
3.3. Fractured CNTs after the tensile test face between Mg matrix and CNTs. Further, since the formation of
Al2MgC2 was less, CNTs could provide the nearly maximum tensile
Fig. 6 shows fractured nanotubes after the tensile test of AZ61 performances.
composite reinforced with 1.37 vol.% CNTs. CNTs were peeled out
from their outer graphene sheets as pointed by white arrows in Acknowledgements
Fig. 6b. This fracture behavior of multi-walled carbon nanotubes
has been already reported in an article [18]. Obviously, the interface The authors greatly appreciate technical supports about TEM
between Mg matrix and CNTs were reinforced enough to effectively observation offered by associate Prof. Makoto Takahashi at Joining
transfer tensile loading from Mg matrix to CNTs. The identified and Welding Research Institution, Osaka University. Also, a part of
Al2MgC2 extended from CNT surface into Mg matrix as shown in the present experiments was carried out using the facilities in the
 H. Fukuda et al. / Composites Science and Technology 71 (2011) 705–709 709

Research Center for Ultrahigh Electron Microscopy, Osaka [9] Ma PC, Siddiqui NA, Marom G, Kim JK. Dispersion and functionalization of
carbon nanotubes for polymer-based nanocomposites: a review. Composites A
University.
– Appl Sci Manuf 2010;41:1345–67.
[10] Fugetsu B, Han WH, Endo N, Kamiya Y, Okuhara T. Disassembling single-
References walled carbon nanotube bundles by dipole/dipole electrostatic interactions.
Chem Lett 2005;34:1218–9.
[1] Iijima S. Helical microtubules of graphitic carbon. Nature 1991;354:56–8. [11] Kondoh K, Serikawa T, Kawabata K, Yamaguchi T. Mg–C films deposited by
[2] Kondoh K, Fukuda H, Umeda J, Imai H, Fugetsu B, Endo M. Microstructural and radio-frequency sputtering. Scripta Mater 2007;57:489–91.
mechanical analysis of carbon nanotube reinforced magnesium alloy powder [12] Viala JC, Claveyrolas G, Bosselet F, Bouix J. The chemical behaviour of carbon
composites. Mater Sci Eng A 2010;527:4103–8. fibres in magnesium base Mg–Al alloys. J Mater Sci 2000;35:1813–25.
[3] Kwon H, Estili M, Takagi K, Miyazaki T, Kawasaki A. Combination of hot [13] Pei ZL, Li K, Gong J, Shi NL, Elangovan E, Sun C. Micro-structural and tensile
extrusion and spark plasma sintering for producing carbon nanotube strength analyses on the magnesium matrix composites reinforced with
reinforced aluminum matrix composites. Carbon 2009;47:570–7. coated carbon fiber. J Mater Sci 2009;44:4124–31.
[4] Shimizu Y, Miki S, Soga T, Itoh I, Todoroki H, Hosono T, et al. Multi-walled [14] Feldhoff A, Pippel E, Wolterdorf J. Interface engineering of carbon-fiber
carbon nanotube-reinforced magnesium alloy composites. Scripta Mater reinforced Mg ± Al alloys. Adv Eng Mater 2000;2:471–80.
2008;58:267–70. [15] Bosselet F, Mentzen BF, Viala JC, Etoh MA, Bouix J. Synthesis and structure of
[5] Goh CS, Wei J, Lee LC, Gupta M. Ductility improvement and fatigue studies in T2–AI2MgC2. Eur J Solid State Inorg Chem 1998;35:91–9.
Mg–CNT nanocomposites. Compos Sci Technol 2008;68:1432–9. [16] Badini C, Ferraris M, Marchetti F. Interfacial reaction in AZ61/AZ91/P100 Mg/
[6] Kondoh K, Threrujirapapong T, Imai H, Umeda J, Fugetsu B. Characteristics of graphite composite: an Auger spectroscopy investigation. Mater Lett
powder metallurgy pure titanium matrix composite reinforced with multi- 1994;21:55–61.
wall carbon nanotubes. Compos Sci Technol 2009;69:1077–81. [17] Feldhoff A, Pippel E, Woltersdorf J. Structure and composition of ternary
[7] Mhlanga SD, Coville NJ. A facile procedure to shorten multiwalled carbon carbides in carbon-fibre reinforced Mg–A1 alloys. Philos Mag A
nanotubes. J Nanosci Nanotechnol 2010;10:5027–35. 1999;79:1263–77.
[8] Qian H, Bismarck A, Greenhalgh ES, Shaffer MSP. Carbon nanotube grafted [18] Bakshi SR, Singh V, McCartney DG, Seal S, Agarwala A. Deformation and
carbon fibres: a study of wetting and fibre fragmentation. Composites A – Appl damage mechanisms of multiwalled carbon nanotubes under high-velocity
Sci Manuf 2010;41:1107–14. impact. Scripta Mater 2008;59:499–502.