Composites Science and Technology 69 (2009) 11931199

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Composites Science and Technology

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Improved processing of carbon nanotube/magnesium alloy composites

Qianqian Li *, Andreas Viereckl, Christian A. Rottmair, Robert F. Singer
Institute of Advanced Materials and Processes, University of Erlangen-Nuremberg, Dr.-Mack-Str. 81, 90762 Fuerth, Germany

a r t i c l e

i n f o

a b s t r a c t
Carbon nanotubes (CNTs) are promising reinforcements for light weight and high strength composites due to their exceptional properties. However, until now, the main obstacle is to obtain a homogenous dispersion of the CNTs in the desired material matrix. Quite a few methods have been studied to help improving the dispersion of CNTs in a polymer matrix. But not much research has been conducted on how to disperse CNTs in metal matrices. In this study, a two-step process was applied. In the rst stage, a block copolymer was used as a dispersion agent to pre-disperse multiwall carbon nanotubes (MWNTs) on Mg alloy chips. Then the chips with the well dispersed MWNTs on their surface were melted and at the same time vigorously stirred. The molten MWNT Mg alloy composites were poured into a cylindrical mould to solidify quickly. For the pre-dispersion step, the microstructures of the Mg alloy chips were studied under SEM. MWNTs were quite successfully dispersed on the surfaces of the Mg alloy chips. The mechanical properties of the MWNT/Mg composites were measured by compression testing. The compression at failure, the compressive yield strength and ultimate compressive strength have all been improved signicantly up to 36% by only adding 0.1 wt% MWNTs to the Mg alloy. In order to predict the potential yield strengths of the MWNT reinforced Mg alloy composites, the contributions by load transfer, Orowan strengthening and thermal mismatch were added up. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 10 December 2008 Received in revised form 11 February 2009 Accepted 15 February 2009 Available online 24 February 2009 Keywords: Melt stirring A. Carbon nanotubes A. Metalmatrix composites (MMCs) A. Nanocomposites B. Mechanical properties

1. Introduction Carbon nanotubes have attracted the attention of many scientists worldwide since their discovery in 1991 [1,2]. Numerical simulations [36] and experimental results [710] have indicated their extraordinary strength (up to 150 GPa) and Youngs modulus (up to 1 TPa), which make them ideal candidates as reinforcements for high strength, light weight and high performance composites. The main problem for CNT composites is to obtain a homogenous dispersion in the matrix materials. Nanoparticles are difcult to disaggregate due to their attractive van der Waals interactions; CNTs have larger surface area ($1000 m2/g) and much higher aspect ratio ($104 normally) than traditional llers. This high specic surface, which is desirable when it acts as an interface for an efcient stress transfer or when maximum resistance against dislocation movement is desired, causes the strong tendency of the CNTs to form agglomerates [11,12]. Carbon nanotubes reinforced polymer based composites have been widely synthesized by repeated stirring, solution evaporation with high energy sonication, surfactant assisted processing and interfacial covalent functionalizations [1316]. Only limited research has been done on carbon nanotube reinforced metal composites. Zhou et al. [17] has reinforced Al composites with carbon

* Corresponding author. Tel.: +49 911 95091833; fax: +49 911 95091815. E-mail address: Qianqian.Li@zmp.uni-erlangen.de (Q. Li). 0266-3538/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2009.02.020

nanotubes by pressureless inltration technique. The hardness of the composites was increased 40% by adding carbon nanotubes. Esawi et al. [18] tried to disperse carbon nanotubes in aluminium powder by mechanical alloying. They also reinforced Al strips with carbon nanotubes by a powder can rolling technique [19]. The Youngs modulus of the composites was increased by 20% after adding 0.5 wt% carbon nanotubes. Carreno-Morelli et al. [20] produced multiwall carbon nanotube/pure magnesium composites by a powder metallurgical method. The results showed that the Youngs modulus was about 9% higher compared to pure Mg metal by adding 2 wt% CNTs. Shimizi et al. [21] fabricated 1 wt% of short and straight carbon nanotubes reinforced Mg alloy composites by a vacuum hot pressure method followed by extrusion. The yield strength, the tensile strength and the Youngs modulus of the CNT/Mg composites have all been improved by about 23%. Beyond simple reinforcement theories based on load transfer, e.g. the rule of mixture, we expect size dependent reinforcement mechanisms to take place. It is the fact that the CNTs have high aspect ratio, which makes it possible to acquire smaller interparticle spacing in the matrix at very low concentrations compared to traditional reinforcements such as SiC. Therefore, CNTs can act as obstacles to dislocation movement in metals. Plastic deformation can only proceed if the dislocations circumvent the obstacle (Orowan mechanism) or shear the nanotube. Because of the small diameter of the CNT, shear appears to be the most likely mechanism. It would mean that dislocations are held up at the CNT and

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Fig. 1. Illustration of the melt stirring machine.

the stress concentration at the head of the pile-up group of dislocations causes the CNT to yield by deformation or fracture. In the case of obstacles with high aspect ratio, dislocations cannot easily climb to circumvent the obstacle, so we expect not only improvements of ow stress and toughness but also a considerable improvement in creep resistance of the material [22]. The investigation of metal matrix composites reinforced with carbon nanotubes has many challenges: 1. A uniform dispersion of CNTs in the metal matrix. 2. A fabrication technique suitable for up-scaling and commercial production. 3. Control of the interfacial reaction between CNTs and the metal matrix. In the present study, a two-step process is designed and applied: step one is a pre-dispersing procedure of CNTs on the Mg, in order to break down big agglomerates; step two is a fabrication of CNT/Mg alloy composite by a melt stirring technique. At step one a block copolymer is used as a dispersing agent to pre-disperse CNTs on Mg alloy chips. The block copolymer was chosen because it has already been proven in previous research that it can improve the dispersion of CNT in ethanol [23,24]. After the CNTs are dispersed on the Mg chips, a straight-forward process a melt stirring technique (see Fig. 1) is used to produce samples. Some research groups have tried to use melt stirring to produce CNT metal composites before [25]. The results showed that the elastic modulus, tensile strength and elongation of the CNT metal composites were all increased. However, in these previous studies the technique was not optimised, CNTs were only stirred into Mg melts without pre-dispersion and the resulting dispersion of the CNTs in the Mg matrix was still uneven [25]. In our study, by combining the pre-dispersion and melt stirring together, we are expecting better dispersion of CNTs and stronger composites.

sonic bath for 15 min. Then it was stirred for 30 min at 250 rpm. After adding Mg alloy chips (AZ91 D, ECKA), the suspension was further stirred at 250 rpm inside a fume cupboard to evaporate ethanol and homogenize the mixture. After the mixture was dried, the MWNT coated chips were placed in a cylindrical sample crucible as shown in Fig. 1. This crucible was placed into an oven and heated up to 650 C under an inert gas atmosphere to avoid oxidation. When the Mg alloy chips were molten, the liquid was mechanically stirred at 370 rpm for 30 min to further disperse MWNTs. After stirring, the molten MWNT/Mg composite was poured into a mould. The cooled sample was machined to cylindrical shaped specimens (diameter 5 mm height 7 mm) for subsequent compression tests. Reference samples were made using exactly the same procedure but from pure AZ91. After the pre-dispersion step scanning electron microscopy (SEM) was used to observe the microstructure on the surface of CNT coated Mg chips. Raman spectrometry was used to detect the CNTs on the Mg chips. The cast composites were cut and polished for grain size measurement by two phase linear analysis method (Leica DMRM, Germany). The resulting samples were tested by compression testing to determine the compression at failure, compressive yield strength and ultimate compressive strength. Tests were conducted at ambient temperature using standard tensile/compression testing equipment (100 kN). Testing was performed at a constant strain rate of 0.01 s1.

3. Results and discussion 3.1. Step 1: pre-dispersion of CNTs on Mg alloy chips For step 1, the pre-dispersion of CNTs on the Mg alloy chips, SEM analysis was used to study the microstructure of the raw MWNTs and the MWNT coated Mg alloy chips. Fig. 2a and b are SEM images of the MWNTs as received. From the images, it can be observed clearly that the raw MWNTs are agglomerated in big bundles. Fig. 2c and d exhibit the SEM images of dispersed MWNTs (white arrows) on Mg alloy chips. At higher resolutions as in Fig. 2e and f, individual MWNTs can be found (white arrows). In order to conrm that the MWNTs we observed under SEM are not damaged, we carried out Raman spectroscopy. In Fig. 3b, we can clearly observe the G band around 1625 cm1, which is characteristic for sp2 bonds in MWNTs. Comparing to the Raman spectra of pristine MWNTs as shown in Fig. 3a, the Raman spectra of MWNT/Mg shows no changes. Therefore, we can conclude that MWNTs are not destroyed during step one and a homogenous dispersion of MWNTs on the Mg chips has been achieved. 3.2. Step 2: fabrication of MWNT Mg composites The well dispersed MWNT coated Mg chips, obtained from step one, were put into the melt stirring equipment and heated up to 650 C under an inert gas atmosphere. When the MWNT/Mg alloy chips were molten, the liquid was vigorously stirred to further disperse MWNTs. After stirring, the molten MWNT/Mg composite was poured into a mould for rapid solidication and then machined into cylindrical shaped specimens for subsequent compression tests. Kim et al. [26] reported that adding carbon to MgAl alloys could effectively contribute to a grain-rening of the matrix. This was explained by the formation of Al4C3 particles which enable heterogeneous nucleation and result in a change of the microstructure. We therefore decided to check whether carbon nanotubes are also acting as a grain rener in the matrix. Fig. 4 shows optical microscopy of the cross sectional area of the pristine AZ91 alloy

2. Experimental The block copolymer Disperbyk-2150 (BYK Chemie GmbH) was rst dissolved in ethanol in a small beaker. Then MWNTs (0.1 wt% of the metal matrix, mass ratio to the block copolymer 1:1, diameter of 520 nm, Baytubes C 150P) were added to the as-prepared solution. This mixture was put at room temperature into an ultra-

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Fig. 2. SEM images of (a), (b) raw MWNTs as received from Bayer, and (c)(f) MWNTs homogeneously dispersed on the Mg alloy chips. The white arrows point at the MWNTs.

Fig. 3. Raman spectra of (a) pristine MWNTs as received, (b) MWNT coated chips and the pure AZ91 alloy chips.

and 0.1 wt% MWNT reinforced Mg composites. As the optical micrographs suggest, there are no obvious grain-rening effects of MWNTs in the Mg alloy matrix. Furthermore, grain sizes of the AZ91 alloy and the 0.1 wt% MWNT reinforced AZ91 composite were measured by two phase linear analysis, i.e. evaluation of the mean intercept. The differ-

ences between the two materials are statistically insignicant as can be seen in Table 1. This result ts with other research [27], in which no change of the microstructure was observed by adding MWNTs. Therefore it can be claimed that the effect of grain size modications due to the presence of CNTs does not play a major role in our CNT composites. There are slight changes in the area

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Fig. 4. Optical microscopy (a) AZ91 alloy, (b) 0.1 wt% MWNT AZ91 composite.

Table 1 Grain sizes of 0.1% MWNT Mg composites and AZ91 alloy. Samples Phase A (a-Mg) Average grain size (lm) AZ91 AZ91 + 0.1 wt% MWNTs 25.6 25.8 Area percentage (%) 86 82 Phase B (eutectic phase) Average grain size (lm) 4.3 5.6 Area percentage (%) 14 18

3.4. Flow strength It is important to understand the strengthening mechanism of CNTs in composites in order to be able to predict the strength. In a rst approach, George et al. [22] summarized three possible reinforcement mechanisms which might be relevant in CNT/metal composite systems, namely load transfer, Orowan looping and thermal mismatch. Furthermore, Zhang et al. [28] has proposed an analytical model to predict the yield strength by incorporating Orowan strengthening effect, enhanced dislocation density strengthening effect due to the thermal mismatch and load bearing effect. Here we simply add up in a linear way all the improvements caused by different mechanisms to predict the theoretical yield strength. The yield strength of the composites by adding MWNTs may be then expressed as:

percentage of a-Mg and the eutectic phase. About 4% more eutectic phase is observed in the MWNT Mg composites compared to the AZ91 alloy. It is not clear whether this is related to adding MWNTs or to the statistical scatter in the process. More experiments will be carried out. 3.3. Mechanical properties of MWNT Mg composites Typical stressstrain curves of the MWNT/Mg composite and the pure AZ91 Mg alloy are shown in Fig. 5a. It is clear that the compression at failure, the compressive yield strength and the ultimate compressive strength were all increased by addition of 0.1 wt% MWNTs. To improve the statistical signicance of the results, 24 specimens were tested following the same procedure. The results are compiled in Fig. 5bd. By adding only 0.1 wt% of MWNTs, the compression at failure (24.4%) has increased 36% compared to the pristine AZ91 Mg alloy (18%) and the ultimate compressive strength of MWNT/Mg composites (412 MPa) increased 20% compared to the pristine AZ91 Mg alloy (344 MPa). Because of the limitation of the measured sample geometry, i.e. the top surface of the cylinder sample was not perfectly parallel to the bottom surface, and the short gauge length (7 mm in our case) in the compression test, 2% yield strength was measured instead of normally 0.2% yield strength to achieve more comparable results. The 2% yield strength of MWNT reinforced Mg composites (272 MPa) is 10% higher compared to the pristine AZ91 Mg alloy (248 MPa). As has been discussed before, no signicant grain-rening effects were observed by adding MWNTs. Therefore the effect of modications in the microstructure of the matrix due to the presence of CNTs is effectively ruled out. The improvement of the mechanical properties of the composites is contributed to excellent mechanical properties of carbon nanotubes. Moreover, combining the SEM observation with the results of our mechanical testing, we attribute the improvement of the compression at failure, the compressive yield strength and the ultimate compressive strength to the good dispersion of MWNTs in the Mg metal matrix.

ryc rym Drload DrOrowan Drthermal

where ryc is yield strength of the nanocomposite; rym is yield strength of the matrix; Drload is the improvement associated with the load transfer effect; DrOrowan is the improvement associated with Orowan strengthening effect; Drthermal is the improvement associated with the increase in dislocation density due to the different thermal expansion coefcients of the matrix and the CNTs (thermal mismatch). The improvements due to load transfer in the simplest form can be written as:

Drload rre mre

where rre is the tensile strength of the carbon nanotubes (strength for MWNTs is suggested in the range of 1163 GPa [29]); mre is volume fraction of the reinforcement. The Orowan strengthening effect is given by:

DrOrowan

0:8 Gm bM Lp

where Gm is the shear modulus of the matrix; b is the value of the Burgers vector of the matrix; M is the Taylor factor (M is chosen to be 3); Lp is the interparticle distance [30]. The CNTs used to reinforce Mg alloy in our experiments have a diameter d of about 13 nm and an average length h of 1 lm, therefore they should be considered as rod-shaped reinforcements. According to research by Ashby [31], Dieter [32], and Kelly [33]:

1 Lp rods p Ns rod

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Fig. 5. (a) Typical compression stressstrain curves of MWNT AZ91 alloy composites (two random samples) and AZ91 (two random samples). Comparison of (b) compression at failure; (c) 2% yield strength and (d) ultimate compressive strength average over 24 samples.

Ns rod

mre
s

where Ns is the number of particles intersecting the slip plane; s is mean area of a slip plane intersected by the rod-shaped particles, d2 and with h ) d, s p2 [34]. Combining Eqs. (4) and (5) we nd:

s pd2 Lp rods 2v re

Finally the hardening due to the thermal mismatch can be expressed as:

Drthermal a Gm b

where a is a geometric constant (1.25 in our case); q is the dislocare DCTED tion density and q Bmb1mre T 1, in which B is a geometric constant d (4 in our case [35]); DCTE is the difference between the coefcient of thermal expansion; DT is the difference between the process and test temperature. In Fig. 6, a comparison of the contributions to the improvement in yield strength by the three strengthening mechanisms is shown as a function of the volume fraction of the MWNTs. It shows that effective Orowan strengthening and thermal mismatch strengthening can already take place at low amounts of MWNTs (about 0.1 wt%) and both contribute almost equally to the improvement of the yield strength. Strengthening due to the load transfer of the MWNTs increases linearly and becomes more important than other strengthening effects at higher MWNTs amounts according to the present model. At a threshold amount of about 0.3 wt% the load transfer effect exceeds the Orowan strengthening and the thermal mismatch effect. The total yield strength affected by the three mechanisms was also plotted in Fig. 6. It demonstrates that the yield strength can in theory be highly increased by the addition of small amounts of MWNTs. We compared our experimental data at 0.1 wt% (0.09 vol%) to this theoretical value. It can be clearly seen that

Fig. 6. Comparison of the strengthening mechanisms and their theoretical contribution to the increase of the yield strength for MWNT/AZ91 composites as a function of MWNT volume fraction, and the experimental 2% yield strength at 0.09 vol% (0.1 wt%) of MWNTs in the Mg matrix.

the experimental data is below the theoretical value, which indicates that the dispersion can still be improved to produce a stronger composite. Further experiments such as producing different samples containing different volume fractions of MWNTs in the matrix are required. It is still not certain which of the mechanisms play a major role in the CNT reinforced metal matrix composites. Eq. (1) faces certain limitations for all three reinforcement mechanisms:  Load transfer: If interfacial shear stresses efciently transfer load from the elastically softer metal matrix to the stronger CNT, this

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Fig. 7. SEM images of the fracture surface of (a) AZ91 and (b) 0.1 wt% MWNT AZ91 composite.

leads to a reduced stress level in the metallic matrix and thus to strengthening. However, this mechanism requires a good interfacial bonding between the CNTs and the metal matrix, which is said to be poor according to other research [3639].  Orowan mechanism: CNTs may act as impenetrable obstacles similar to non-shearable precipitates and increase the yield stress through an Orowan mechanism. Again, there is no specic study of the interfacial processes characterizing the interaction between a dislocation and a CNT. In particular, it is not clear whether dislocation motion indeed requires the formation of Orowan loops, or whether the strain caused by the shearing of the metal around the CNT can be accommodated by plastic deformation or fracture of the CNT, leading to a quasi-cutting mechanism of dislocation motion.  Thermal mismatch hardening: There is a signicant mismatch in coefcient of thermal expansion between CNT and the matrix, and this might be accommodated by extensive dislocation nucleation around CNT which then leads to hardening of the metal matrix. However, it is not at all clear to which extent the analysis of Arsenault [35], which relates to SiC platelets with sizes and separation distances of the order of several microns, can be applied to the quite different scale and geometry of embedded CNT. Due to these limitations, further understanding is clearly necessary. The behaviour of CNTs in the metal matrix needs to be studied and characterization of such composites by different methods is required. 3.5. Ductility From the compression test results, one notable observation is that the compression at failure, i.e. the ductility, increased (as much as 36%) together with the strength. This is different from what is observed when using traditional reinforcements such as carbon bres [40]. Fig. 7 shows SEM images of the fracture surface of AZ91 alloy and the 0.1 wt% MWNT reinforced AZ91 alloy. It is obvious that the AZ91 alloy has a rather smooth fracture surface with several sharp breaking edges, while the fracture surface of MWNT reinforced AZ91 composite exhibits a lot of dimples, which indicates a more ductile behaviour of the composite. Increased ductility has also been found in CNT reinforced Mg composites before by Goh [41]. Their explanation for this is the activation of prismatic slip planes in the Mg matrix by adding CNTs. It implicates a minimum of ve independent slip systems which are required to deform a polycrystalline metal plastically (von Mises criterion), therefore resulting in a much

higher ductility of the composites. This idea was further conrmed by TEM studies [30]. A high activity of the basal slip system and the initiation of prismatic slip at room temperature were observed under TEM. 4. Conclusions In this study, a two-step process was designed and applied. Multiwall carbon nanotubes were rst dispersed on the Mg alloy chips using a block copolymer as a dispersion agent. In this step, the agglomerates of MWNTs were separated. Then the MWNT coated Mg chips were used to fabricate CNT/Mg alloy composites by a melt stirring technique. A good dispersion of MWNT in the Mg matrix was achieved by this two-step process. After step one, we conrmed by Raman spectroscopy that MWNTs were still intact on the surface of the Mg chips. Under SEM, individual multiwall carbon nanotubes can be found on the surface of Mg chips after the dispersion stage. Adding a small amount of multiwall carbon nanotubes significantly enhanced the mechanical properties of the AZ91 Mg alloy. Compared to the AZ91 Mg alloy, the compression at failure of the MWNT/Mg composites was improved by 36%; the 2% yield strength was improved by 10% and the ultimate compressive strength was improved by 20%. Unlike in the case of adding traditional reinforcements, the compression at failure was improved in addition to the other properties. We attribute the improvement of the mechanical properties to the homogenous dispersion of MWNTs in the Mg matrix. No change in grain size has been measured between the composites and the pristine AZ91 alloy, which indicates that MWNTs do not act as a grain rener in the matrix. The contributions of load transfer, Orowan strengthening and thermal mismatch were simply added up to predict the potential yield strengths by adding different volume fractions of MWNTs to the composites. The experimental result of 2% yield strength at 0.09 vol% (0.1 wt%) was compared to the theoretical value. It showed that the dispersion still needs to be improved to produce a stronger material. It is still not certain which mechanisms play a main role in the strengthening of the carbon nanotube reinforced metal composites. Further understanding is required. Further studies such as: detailed observation on the microstructure and elemental composition together with SEM and TEM investigations of fracture surfaces and the alloyMWNT interface; producing different samples with different volume fracture of MWNTs, will also be undertaken in the future and presented in a separate paper.

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Acknowledgements A nancial grant of the Bavarian State Ministry of Science, Research and Arts and the Objective 2 Funding of the European Union are gratefully acknowledged. We would like to thank Christian Rauber for his great help and suggestions through the experiments; also thanks to Florian Pyczak, Jens Schauer and Natalie Kmpel for their kind technical assistant. We are indebted to Bayer AG, BYK Chemie GmbH and ECKA Granulate GmbH & Co. KG for their generous offers of the materials used in this study. We greatly appreciate Prof. Michael Zaiser and Dr. Jan Schwerdtfeger for fruitful discussions and suggestions. References
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