phys. stat. sol. (a) 201, No. 8, R53 R55 (2004) / DOI 10.1002/pssa.

200409045

Carbon nanotube/magnesium composites

E. Carreo-Morelli*, 1, J. Yang2, E. Couteau2, K. Hernadi2, J. W. Seo2, C. Bonjour1, L. Forr 2, and R. Schaller2
1

University of Applied Sciences of Western Switzerland, Design & Materials Unit, 1950 Sion, Switzerland Swiss Federal Institute of Technology Lausanne, Institute of Physics of Complex Matter, 1015 Lausanne, Switzerland

PACS 61.46.+w, 81.05.Ni, 81.05.Zx, 81.07.De Novel magnesium matrix composites reinforced with carbon nanotubes have been processed by powder metallurgy. Blends of metal powders and multi-wall carbon nanotubes were compacted by uniaxial hot pressing followed by hot isostatic pressing. A uniform dispersion of nanotubes in the metal matrix was obtained. A coating method of nanotubes is described, which is promising to improve the matrixreinforcement bonding strength.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction High stiffness and very low density make carbon nanotubes (CNTs) good candidates for use as reinforcements in composite materials [1]. CNTs can be produced by arc-discharge methods, laser ablation or catalytic chemical vapor deposition (CVD). Arc-discharge and laser ablation CNTs are the ultimate high strength fibers with Youngs modulus up to 1.2 TPa [2], but they cannot yet be produced in large-scale. Catalytic CNTs are one order of magnitude less stiff [3], but they offer the greatest potential for production up-scaling. In recent years, much research has been devoted to the development of nanotube-reinforced polymers and ceramics. On the other hand, only few studies have been concerned with nanotube-reinforced metals, which remains almost a virgin field [1, 4]. In this work, novel metal matrix composites are processed by powder metallurgy of catalytic CNT/light-metal blends. 2 Experimental Multi-wall carbon nanotubes were processed by catalytic decomposition of acetylene in a fixed-bed flow reactor at 720 C over 5% Co, Fe/CaCO3 catalyst [5]. Commercially available magnesium powder (99.8% purity, average particle size 38 m, Alfa Aesar) was used as base metal powder. Mg2wt%CNT powder mixtures where prepared by dry blending for 4 h in a Turbula T2C mixer. Ceramic balls were used during mixing to mill CNT agglomerates and improve mixture homogeneity. The blends were placed in a double-action graphite tooling consisting of a die and two cylindrical pistons. Disk-shaped compacts ( 53 mm 5 mm) were obtained by hot pressing at 600 C in a vacuum atmosphere, under a pressure of 50 MPa for 30 min. Finally, the compacts where hot isostatic pressed at 600 C for 60 min under an argon pressure of 1800 bar. The density of the sintered parts was measured by the Archimedes method.

Corresponding author: e-mail: efrain.cmorelli@hevs.ch, Phone: +41 606 88 37, Fax: +41 606 88 15
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

physica status solidi

Received 23 April 2004, revised 17 May 2004, accepted 18 May 2004 Published online 25 May 2004

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E. Carreo-Morelli et al.: Carbon nanotube/magnesium composites Fig. 1 Stress-strain behavior of Mg 2wt%CNT composites measured in tensile tests.
0.2 = 89 MPa TS = 140 MPa f ~ 3 %

140

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stress [MPa]

100 80 60 40 20 0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

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Mechanical properties where evaluated by tensile tests and Youngs modulus measurements in a resonant bar apparatus, which allows one to tune the resonant frequency f (in the kHz range) in flexural mode for specimens 4 mm 1 mm 50 mm. The Youngs modulus E is given by [6]
E = 0.943 l4 f 2, a2

where l and a are the specimen length ant thickness respectively, and is the density. Specimens where obtained by spark-machining. Scanning electron microscopy observations were performed in a Philips XL 30 FEG microscope. 3 Results and discussion The measured density of the sintered compacts is up to 98% of the theoretical density calculated from a mixture law. Resonant measurements show an improvement of about 9% in the Youngs modulus of Mg2wt%CNTs (38.6 0.7 GPa) compared with unreinforced sintered Mg (35.3 0.8 GPa). The stress-strain curves measured in tensile tests (Fig. 1) exhibit a ductile metallic behavior, which suggests good bonding between carbon nanotubes and magnesium matrix. The yield strength 0.2, rupture strength TS and strain after fracture f, are similar to those measured in sintered magnesium. Scanning electron microscopy of the fracture surface of a Mg2wt%CNT specimen (Fig. 2) reveals that carbon nanotubes are uniformly dispersed in the magnesium matrix. This uniform dispersion of reinforcement, together with the overall performance of the processed composites show that potential sources of weakness as nanotube agglomerates can be avoided by appropriate mixing and sintering. Further improvement of mechanical properties will be related with (a) the use of electric-arc discharge processed multi- or single-wall nanotubes instead of CVD processed nanotubes and (b) the improvement

Fig. 2 Microstructure of a rupture surface of Mg2wt%CNTs.

2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (a) 201, No. 8 (2004) / www.pss-a.com

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b
Mg K

Cu L Ti K

Energy (keV)

of interface bonding strength to guarantee load transfer from the matrix to the reinforcement. In a previous work [3], it has been shown by AFM measurements of the Youngs modulus that catalytic CNTs exhibit poor mechanical properties compared with arc-discharge CNTs. The problem is that, at the moment, the arc-discharged technique cannot be used for large-scale production. On the other hand, interface bonding strength can be improved by applying appropriate surface treatments to the nanotubes. Recently, an homogeneous coating of nanotubes with various inorganic materials as alumina, silica and titania has been obtained [7]. In the present research, the focus was on metallic Mg coatings. Purified multi-wall CNTs were used as raw or modified by surfactant (sodium dodecyl sulfate, SDS). The impregnation was carried out with and without solvent (isopropanol) for both types of CNTs. As magnesium sources, three compounds, namely magnesium ethoxide (Mg(OC2H5)2, Mg(OEt)2) and MgCl2 were applied. When MgCl2 source was applied, a thick layer of amorphous magnesia was obtained over SDStreated CNTs, whereas the use of plain CNTs resulted in a few tubes showing slight coverage. Moreover homogeneous coverage of Mg was obtained on plain CNTs when the impregnation was carried out using organometallic and inorganic sources. Figure 3a shows a representative TEM image of a plain multi-wall CNT after coating with Mg. The coating is about 2 nm thick and the nanotube is homogeneously covered. EDX analysis clearly confirms the presence of Mg as coating material (Fig. 3b). 4 Concluding remarks Carbon nanotube reinforced magnesium has been processed by dry blending of base powders followed by hot pressing and hot isostatic pressing. A uniform dispersion of nanotubes in the magnesium matrix has been obtained. The same processing steps have been used to process Al2wt%CNT up to 96% of the theoretical density. In addition, a coating method of nanotubes with magnesium was developed, which is intended to improve interface bonding strength in sintered compacts.
Acknowledgements This work was supported by the Swiss Innovation Promotion Agency under CTI Contract No. 5990.3 TNS, and by the European TMR network NANOCOMP.

References
[1] [2] [3] [4] [5] [6] [7] E. T. Thostenson, Z. Ren, and T.-W. Chow, Compos. Sci. Technol. 61, 1899 (2001). F. T. Fischer, R. D. Bradshaw, and L. C. Brindson, Compos. Sci. Technol. 63, 1689 (2003). J.-P. Salvetat et al., Adv. Mater. 11, 161 (1999). C. L. Xu, B. Q. Wie, R. Z. Ma, J. Liang, X. K. Ma, and D. H. Wu, Carbon 37, 855 (1999). E. Couteau et al., Chem. Phys. Lett. 378, 917 (2003). B. Vittoz, B. Secrtan, and B. Martinet, J. Appl. Math. Phys. 14, 46 (1963). K. Hernadi, E. Ljubovic, J. W. Seo, and L. Forr, Acta Mater. 51, 1447 (2003).
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Fig. 3 a) TEM micrograph of a multi-wall CNT with Mg coating. White arrows indicate the homogeneous coating of Mg with a thickness of 2 nm. b) EDX-spectrum reveals a significant peak of Mg. Cu peaks are due to the TEM grid used as sample supporting grid; the Ti peak is an artefact of our EDX set-up. No significant peak of O K at 0.523 keV is visible.

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Cu K

Intensity (arb. unit)