Scripta Materialia 53 (2005) 11591163 www.actamat-journals.

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Strengthening in carbon nanotube/aluminium (CNT/Al) composites

R. George *, K.T. Kashyap, R. Rahul, S. Yamdagni
Mechanical Engineering, MS Ramaiah Institute of Technology, MSRIT post, Gokula, Bangalore, Karnataka 560 054, India Received 1 June 2005; received in revised form 7 July 2005; accepted 19 July 2005 Available online 15 August 2005

Abstract Carbon nanotubes (CNT) have a Youngs modulus of 1 TPa, making them ideal reinforcements for composite materials. It is important to understand the relevant strengthening mechanisms involved in CNT/Al composites, in order to produce optimized composites. Three major mechanisms are analyzed along with experimental procedure for making CNT/Al composites. 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Carbon nanotubes; Powder processing; Transmission electron microscopy; Metal matrix composite; Mechanical properties

1. Introduction Carbon nanotubes (CNT) and their mechanical properties have been closely investigated since the late 1990s. Theoretical work [13] and experimental results [46] have indicated their extraordinary stiness and strength, which are unparalleled by any other material available today. Results show that single-walled nanotubes (SWNTs) have Youngs moduli ranging from 1 to 5 TPa, while multiwalled nanotubes (MWNTs) show an average value of 1.8 TPa. These results can be compared with the theoretical Youngs modulus of the basal plane of graphite, which is 1 TPa. Thus, CNTs being defect free and possessing low dislocation density provided the driving force behind the development of CNT/Al composites. In addition, CNTs possess relatively low density, varying from $1.2 g/cm3 for SWNTs up to 1.8 g/cm3 for MWNTs, compared to 2.26 g/cm3 for graphite [7]. This gives CNTs a high specic strength of 55.55 GPa/ (mg/m3) and high specic modulus of 555.55 GPa/ (mg/m3), which makes them ideal reinforcements in composites.
*

Although CNTs present a novel reinforcement with redoubtable mechanical properties, metal matrix composites with CNT reinforcement remain in their infancy, with only a few papers on the subject [810]. This may be primarily due to the processing diculties and lack of understanding of the strengthening mechanism involved. The present paper addresses the processing of CNT/ Al composites, mechanical characterization and the strengthening of the composites associated with various mechanisms. The three mechanisms put forward are thermal mismatch, Orowan looping and shear lag theory. It is the objective of the present paper to identify the mechanism of strengthening of CNT/Al composite.

2. Experimental procedure Multiwalled and single-walled nanotubes were synthesized by arc evaporation method. MWNT. An electric arc was struck between a graphite anode and a copper cathode of respective diameters 7 mm and 12 mm in a helium atmosphere of 500 Torr. A cylindrical deposit grew on the copper cathode and consisted of a hard gray outer shell and a soft brous black core. The soft core mainly consisted of MWNTs.

Corresponding author. Tel.: +91 80 9845 318047. E-mail address: rgeorgemsrit@redimail.com (R. George).

1359-6462/$ - see front matter 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.scriptamat.2005.07.022

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SWNT. The graphite rod was drilled axially and densely packed with a mixture of nickel and iron 5% (1:1) and 95% graphite powder. The helium pressure is maintained at 100200 Torr. SWNTs were formed as a web like structure in the arc discharge chamber and also in the collar around the cathode. TEM images of MWNT and SWNT are shown in Fig. 1(a) and (b), respectively. 2.1. Composite preparation Powder metallurgy technique was used for composite fabrication. CNTs (MWNT and SWNT) were dispersed in ethanol and sonicated for 20 min. The decanted solution was heated to vaporize ethanol and the residue was used as the reinforcement material. Commercial purity aluminium was used as the matrix material. A mixture of CNT and aluminium powder (200 mesh) were ball milled at 200 rpm for 5 min. The short duration and slower milling speed ensures that the carbon nanotubes are intact and can be validated from the transmission electron microscopy (TEM) images of the composite shown in Fig. 5(a) and (b). The milled powder was compacted in a circular die with a load of 120 KN; the billets thus obtained were sintered in an inert gas environment (nitrogen) for 45 min at 580 C and nally hot extruded at 560 C. Some samples were also prepared with K2ZrF6 coated CNTs. This coating was added by rst dissolving the salt in boiling distilled water, and then adding CNT powder. The water was allowed to evaporate o, leaving behind a residue, which was used in subsequent composite preparation. 2.2. Raman spectroscopy SWNTs. The radial breathing mode (RBM) of a SWNT is Raman active because of its symmetry. The Raman spectrum (i.e., intensity vs. Raman shift) of a

sample of SWNT is a direct probe of the allowed RBMs and of the diameter distribution. The diameter dependence of the RBM [11],  238=d 14 c 1

where  wave number of RBM in cm1 , d = SWNT c diameter in mm. From the RBM mode (166.3 cm1) of the Raman spectra shown in Fig. 2, the average diameter of SWNT from Eq. (1) is 1.56 nm. MWNTs. Raman spectroscopy has been used for characterizing MWNTs [10,11]. The spectrum for MWNTs is quite dierent compared with SWNTs and consists of a disorder (D-band) and tangential band (G-band) that appear around 1348 cm1 and 1590 cm1 (Fig. 3), respectively. The tangential bands show no splitting as seen in SWNTs and appear very much like G-band graphite.

Fig. 2. Raman spectra of SWNTs.

Fig. 1. TEM images of (a) MWNT (b) SWNT (scale bar 50 mm).

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iumcarbon nanotube composites, there exists a signicant coecient of thermal expansion mismatch between the matrix and the carbon nanotubes, which would result in prismatic punching of dislocations at the interface, leading to work hardening of the matrix. The dislocation density that is generated is dependent on the reinforcement surface area. Carbon nanotubes have an advantage due to their small diameter leading to a lower density of Grith aws. The dislocation density generation is likely to be higher, which in turn would result in increased strengthening. Dislocation density (q) is given by q 10 A=bt1 A
Fig. 3. Raman spectroscopy of MWNT.

3. Results and discussion The carbon nanotube quality was gauged from Raman spectroscopy, shown in Figs. 2 and 3. The MWNT and SWNT synthesized by arcdischarge shows good graphitization and no structural defects. The composites prepared showed a densication of 98% post sintering. X-ray diraction of the composite samples (with and without K2ZrF6) shows no major aluminium carbide phase formation. The X-ray diraction patterns are overlapped and shown in Fig. 4. 3.1. Strengthening mechanisms Based on the geometry and physical properties of multiwalled nanotubes, three strengthening mechanisms were considered for the CNT/Al composite system, namely thermal mismatch, Orowan looping and shear lag models. These models are presented in brief below. 3.1.1. Thermal mismatch [12] This is an extension of the Arsenault model for silicon carbide reinforced aluminium. Carbon nanotubes have a coecient of thermal expansion of $106 K1, which is considered to be the same as graphite; while commercial purity aluminium exhibits a much greater coecient of thermal expansion of 23.6 106 K1. Thus in alumin-

where A is the reinforcement (carbon nanotube) volume fraction,  is thermal strain, b is Burgers vector, and t is the dimension of the reinforcement (carbon nanotube). Incremental strength of the composite, Dr alq1=2 b 3

where a = constant = 1.25, l is the modulus of rigidity of the matrix (Al), b is Burgers vector. 3.1.2. Orowan looping [13] In this mechanism the motion of the dislocations is inhibited by nanometer sized carbon nanotubes, leading to bending of these dislocations between the carbon nanotubes. This produces a back stress, which will prevent further dislocation migration and result in an increase in yield stress. The Orowan looping mechanism is important in aluminium alloys, which are strengthened by ne precipitates. However, this strengthening mechanism rarely has any real signicance in metal matrix composites as the reinforcements are generally coarse and inter-particle spacing is large. But since carbon nanotubes eectively represent very ne particles, perpendicular to the tube axis, in the order of a few nanometers, it strengthens the aluminium matrix. Further, due to their high strength the shearing of carbon nanotubes is not the determining factor for the composite strength. Particle shearing usually restricts the maximum strengthening that can be achieved by this method. Incremental shear strength of the composite, Ds Constant lbA1=2 =r ln2r=r0 where r is the radius of reinforcement (carbon nanotube), constant = 0.093 for edge dislocation and 0.14 for screw dislocation, r0 is the core radius of dislocation = 3.5 109 m, b is Burgers vector, l is modulus of rigidity of matrix (Al) = 2.64 1010 N/m2, and r is the volume equivalent radius = 1.593 107 m for MWNT and 7.087 109 m for SWNT. 3.1.3. Shear lag [14] This model involves the transfer of load from the matrix to the reinforcement by interfacial shear stress. Thus

Fig. 4. XRD of composite samplesshowing a clear overlap.

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the stiness of the carbon nanotubes is directly utilized. High aspect ratio reinforcements are favored with this model. However, aspect ratios greater than s = 100 provide no signicant advantage. Aspect ratios of multiwalled nanotubes are in the $100 range while that of single-walled nanotubes is extended to $1000. Of course wetting is a necessary condition for interfacial shear stress transfer; this is likely to be a major concern with aluminiumcarbon nanotube composites. Carbon nanotubes have been reported to show a surface tension of 100200 mN/m [15,16]; while the surface tension of aluminium is 865 mN/m. Clearly, there seems to be an irreconcilable dierence in these values. Fortunately, in carbon ber composites manufacturing, it is common practice to use K2ZrF6 in order to improve bonding between graphite and aluminium. Due to structural similarities between graphite and carbon nanotube it is quite likely that this salt can be used with aluminium carbon nanotube composites for the same eect. The Youngs modulus (Ec) of the composite is Ec AEf 1 tanhns=ns 1 AEm 4 where Ef is the Youngs modulus of the reinforcement (carbon nanotube), n 2Em=Ef 1 cm ln1=A
1=2

Em is the Youngs modulus of matrix (aluminium), s is the aspect ratio of reinforcement (carbon nanotube), A is reinforcement (carbon nanotube) volume fraction, cm = Poissons ratio of aluminium matrix, and aspect ration s = 100 for MWNT and 500 for SWNT. Calculations from the above theoretical models and the experimental data are depicted in Tables 1 and 2. Commercial purity aluminium under the same processing and testing conditions as that of the composites

has yield strength (YS) of 80 MPa and a Youngs modulus of 70 GPa. It is important to note that only selected data is shown due to the fact that many samples suered from breakage at grips, during tensile testing on an Instron machine. Multiwalled/aluminium composite showed an increase in the Youngs modulus with an increase in volume fraction (VF) of the reinforcement. For 0.5% VF of MWNTs, Youngs modulus increased by 12% and for 2% a 23% increase was seen. These values correlate with Youngs modulus of shear lag model as shown in Table 1. The experimental results indicate no abnormal increase in the Youngs modulus with and without addition of K2ZrF6 One could conclude with the available results that the wetting agent hardly plays a role in stiening this composite. This is in contradiction of the fact that CNT cannot wet aluminium due to the large dierence in their surface energies [16]. From Table 1 the yield strength values from the experimental results and Orowan looping mechanism correlate closely. However there is a large variation with respect to the thermal mismatch model. Single-walled/aluminium composite does not show a considerable increase in Youngs modulus with an increase in VF of reinforcement as was seen in multiwalled/aluminium composite. However, interestingly enough the addition of K2ZrF6 as wetting agent results in an increase of 33.85% in the stiness of the composite as shown in Table 2. This indicates that the wetting agent plays a crucial role in the transfer of load from the aluminium matrix to the SWNT reinforcement. The Youngs modulus of this composite is much higher than in the theoretical shear lag model whereas the composites without the wetting agent show a much better correlation with the shear lag model.

Table 1 Comparison of theoretical and experimental data for MWNT/Al composite MWNT % volume fraction 0.5 0.5 + K2ZrF6 2 Shear lag Youngs modulus, GPa 74.305 74.305 87.376 Experimental Youngs modulus, GPa 78.1 75.20 85.85 Thermal mismatch yield strength, MPa 117.346 117.346 197.346 Experimental yield strength, MPa Orowan looping yield strength, MPa 90.573 90.573 101.145 Experimental ultimate tensile strength, MPa 134 150 138

86 93 99

Table 2 Comparison of theoretical and experimental data for SWNT/Al composite SWNT % volume fraction Shear lag Youngs modulus, GPa 79.167 79.167 88.355 Experimental Youngs modulus, GPa 70 93.7 79.3 Thermal mismatch yield strength, MPa 471.403 471.403 636.344 Experimental yield strength, MPa 79.8 98.7 90.8 Orowan looping yield strength, MPa 184.203 184.203 227.365 Experimental ultimate tensile strength, MPa 141 181 134

1 1 + K2ZrF6 2

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Fig. 5. (a) TEM image of MWNT/A1 composite with K2ZrF6. (b) TEM image of MWNT/A1 composite.

The YS values of SWNT/Al composite show a mismatch with theoretical predicted values from Orowan looping and the thermal mismatch model. Bright eld TEM images of composite shown in Fig. 5(a) and (b) reveal that carbon nanotubes have pinned the sub grain boundaries of the aluminium matrix. It is also observed that there are no free dislocations in the sub grains, probably due to the dislocations being captured by low angle tilt or twist boundaries at the sub grain as these experience reduced energy. It is also interesting to observe that dislocation loops, which are indicative of Orowan looping, are absent on the carbon nanotubes. This behaviour may be due to the collapse of the dislocation loops at the CNT/aluminium interfaces. It is dicult to identify the mechanism of strengthening in CNT/Al composite from TEM images since aluminium possessing high stacking fault energy dynamically recovers during deformation due to which evidence of the mechanisms discussed above are lost.

Acknowledgements The authors express their sincere gratitude to the principal, management and faculty of M.S. Ramaiah Institute of Technology, Bangalore for their support and encouragement. The authors also express their sincere gratitude to the Ministry of Defence, DRDO for their funding of this project (No. ERIP/ER/0304268/ M/01). Finally, the authors appreciate the technical support extended by Indian Institute of Science Bangalore, DMRL Hyderabad and BARC Bombay.

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4. Conclusion The results have shown that mechanical properties of the CNT/Al composite, including Youngs modulus, have shown improvement. With the increase in Youngs modulus clearly the shear lag model seems to be applicable, since the other two models are not associated with Youngs modulus, but an increase in yield strength could imply the additional applicability of Orowan looping and thermal mismatch models to the composite system. Hence the strengthening of the composite could be due to the synergistic eect of these mechanisms. However, TEM images do not reveal any direct evidence for these mechanisms.