Composites Science and Technology 72 (2011) 103111

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Composites Science and Technology

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Fabrication and characterization of Al-matrix composites reinforced with amino-functionalized carbon nanotubes
S.K. Singhal a,, Renu Pasricha b, Satish Teotia c, Girish Kumar d, R.B. Mathur a
a

Physics & Engineering of Carbon, National Physical Laboratory (Council of Scientic & Industrial Research), Dr. K.S. Krishnan Road, New Delhi 110 012, India Electron & Ion Microscopy, National Physical Laboratory (Council of Scientic & Industrial Research), Dr. K.S. Krishnan Road, New Delhi 110 012, India c Guru Jambeshwar University of Science and Technology, Hisar, India d Jamia Millia Islamia, New Delhi 110 002, India
b

a r t i c l e

i n f o

a b s t r a c t
We report the fabrication of Al-matrix composites reinforced with amino-functionalized carbon nanotubes (fCNTs) using powder metallurgy process. Functionalization of the nanotubes was carried out by ball milling multiwalled carbon nanotubes (MWCNTs) in the presence of ammonium bicarbonate. It has been found that the mechanical properties of Al-fCNT composites were much superior to the composites fabricated using non-functionalized or acid functionalized carbon nanotubes. The enhancement in mechanical properties in these composites are attributed mainly to the better and homogeneous dispersion of fCNT in Al matrix as compared to non-functionalized or acid functionalized carbon nanotubes and the formation of a strong interfacial bonding between fCNT and Al matrix leading to an efcient load transfer from Al matrix to fCNT following high-resolution transmission electron microscopy. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 23 September 2010 Received in revised form 4 June 2011 Accepted 14 October 2011 Available online 21 October 2011 Keywords: A. Metal-matrix composites (MMCs) A. Carbon nanotubes B. Mechanical properties D. Scanning/transmission electron microscopy (STEM) E. Sintering

1. Introduction Since the discovery of carbon nanotubes (CNTs), signicant works have been carried out in recent years to use these nanotubes for various industrial applications because of their unique mechanical, thermal and electrical properties [13]. One of the most promising uses of CNT is the reinforcement of composite materials to overcome the performance limits of conventional materials. Multiwalled carbon nanotubes (MWCNTs) have great potential applications due to their large aspect ratio (100010,000) [4], low density ($1.8 g/cm3), high Youngs modulus of the order of 1.8 TPa [5,6], and high tensile strength up to 150 GPa [7]. All these properties make MWCNT one of the most suitable candidates for the reinforcement of a variety of materials. Recent developments in MWCNT/polymer composites have shown the potential for improving the strength of polymers [810] and this nding has encouraged researchers to use carbon nanotubes as reinforcements for metal and ceramic matrices. However, because of the difculties in distributing MWCNT homogeneously in a metal or ceramic matrix by means of traditional composite processes, it has been doubted whether MWCNT can really reinforce metal or ceramics. In the area of metal composites, Al has attracted intense interest because of its excellent strength, low density and corrosion
Corresponding author. Tel.: +91 11 45608404; fax: +91 11 45609310.
E-mail address: sksinghal@mail.nplindia.ernet.in (S.K. Singhal). 0266-3538/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2011.10.007

resistance properties. The combination of unique properties of MWCNT and Al has, therefore, substantial potential in many weight sensitive applications such as aerospace & automobile sectors though still considerable research is needed to identify optimal processing route. Thus, only few researchers have explored MWCNT reinforced Al composites, which are mainly attributed to the processing difculties and lack of understanding of the strengthening mechanisms and, therefore, no major breakthrough has been made. One of the key problems in the fabrication of AlMWCNT composites is the homogeneous dispersion of MWCNT throughout the Al matrix and strong interfacial bonding to ensure a better load transfer from the nanotubes to Al matrix. This is mainly due to the fact that MWCNT have tremendous surface area of up to 200 m2 g1 which leads to the formation of clusters due to very strong van der Waals force of attraction between them. Therefore, the main researches in the fabrication of these composites are focused on homogeneous dispersion of MWCNT in Al matrix and bonding at the Al/MWCNT interface. Clustering leads to concentration of reinforcement at certain points and this could lead to worsening of overall mechanical properties. In this direction several methods were tried in order to obtain a homogeneous dispersion of MWCNT such as high energy ball milling [11], use of COOH/OH functionalized MWCNT [12] or using some surfactants such as sodium dodecyl sulfate [13,14] in order to decrease the van der Waals force of attraction between them and to facilitate their ease of dispersion, molecular-level mixing [15], chemical

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vapor deposition (CVD) [16] in which MWCNT with a low Ni content were grown on Al powder using CVD and use of natural rubber by nanoscale dispersion [17]. In spite of the difculties of obtaining a homogenous dispersion of MWCNT in Al matrix, several processes have been tried to develop MWCNT reinforced Al -matrix composites including powder metallurgy (PM) route [1725], roll bonding followed by annealing [26], plasma spray forming [27], liquid inltration [28] and high pressure torsion [29]. Of all the process mentioned above, only PM route has been found to be very effective for producing MWCNT reinforced Al matrix composites of any size and shape on a large scale. This process mainly consists of mixing MWCNT with Al powders either in dry or wet conditions followed by consolidation by compaction and sintering, cold isostatic pressing, hot isostatic pressing or spark plasma sintering. In most of these processes, the composite compacts were subjected to post-sintering deformation processes such as rolling, extrusion or equal channel angular processing [30]. Although high energy ball milling has been found to be effective to obtain homogeneous dispersion of MWCNT in Al matrix [11], various process parameters e.g. milling time, speed, ball to powder weight ratio are still not very much clear and need further investigations. Also the nature of functionalized MWCNT for better dispersion and the interfacial bonding between MWCNT and Al matrix in the composites are still not very clear. Keeping in view of these facts, in the present paper, we report the fabrication of Al matrix composites reinforced with amino-functionalized carbon nanotube (fCNT) using powder metallurgy route. The dispersion of fCNT in Al powder was found to be much better as compared to those of non-functionalized MWCNT. fCNT were synthesized by ball milling MWCNT in the presence of ammonium bicarbonate (NH4HCO3). It must be mentioned that although fCNT have been used in the fabrication of polymer composites they have not been used in the fabrication of Al-matrix composites to the best of our knowledge. A possible mechanism of the functionalization of MWCNT with amine and amide groups is also discussed in detail. The process could be useful for producing these composites on a large scale, as it is simple and effective.

almost one hour. A drop of the well dispersed solution from the top layer was drop casted on the carbon coated copper grid and allowed to dry. The samples were characterized using Tecnai G2 F30 S-Twin (FEI; Super Twin lens with Cs = 1.2 mm) instrument operating at an accelerating voltage at 300 kV, having a point resolution of 0.2 nm and lattice resolution of 0.14 nm.). Program Digital Micrograph (Gatan) was used for image processing. Thermo-gravimetric analysis (TGA) was carried out to determine amorphous carbon (if any) and iron present in MWCNT. These experiments were carried out using a TGA equipment (Model: 1/1600/LS TGADTA), Mettler-Toledo, Switzerland). The ow rate of air was kept constant at 80 ml/min and the samples were heated from 30 to 1000 C at a rate of 10 C/min. Raman spectroscopy was utilized to understand the structure of MWCNTs and fCNTs. The spectra were collected under ambient conditions using 633 nm helium neon laser. A Universal Testing Machine (Instron Model: 4411) was used to measure the compressive strength of composites at room temperature under a constant strain rate of 0.008 mm/s. 2.2. Fabrication of Al- fCNT composite powders A homogeneous mixture of fCNT and Al powder was made by mixing 0.53.0 wt.% fCNT with Al powder by ultrasonication for 3 h in toluene followed by drying using a magnetic stirrer. About 4.4 g of this mixture was transformed into a stainless steel container containing 6 stainless steel balls (10 mm diameter). About 2 wt.% of stearic acid, used as a process control agent (PCA) was also added to the mixture to prevent agglomeration of Al powder. The balls to powder weight ratio was 10:1. The mixture was ball milled at a speed of 323 rpm for 515 h using a planetary ball mill in presence of Ar lled in the container at a pressure of 300 kPa. After milling, the container was opened very slowly to collect the Al-fCNT composite powders. The dispersion of fCNT in Al powder was studied using scanning electron microscopy (SEM). 2.3. Consolidation of Al- fCNT composites A homogeneous mixture containing fCNT and Al powders was pressed on a uniaxial press in a rectangular shaped die of size 13 7 mm at a pressure of 500600 MPa for 5 min. Subsequently, the obtained bulk was sintered at 550620 C for 23 h under a vacuum of $102 torr using a vacuum sintering furnace. The heating and cooling rates were adjusted to about 20 and 10 C/min respectively. The sintered composites were polished well using a ne diamond paste and various mechanical and other characterizations were made. 3. Results and discussion 3.1. Characterization of pure and fCNT The dispersion of fCNT in Al powder was studied using SEM. Fig. 1a and b shows a SEM image and an XRD pattern of pure MWCNT used for its functionalization. It can be seen that the as produced MWCNT are quite long and entangled. Their diameter was in between 20 and 50 nm and length about few tens of microns. Most of the nanotubes were not straight and very exible. The d002 of the MWCNT was 0.345 nm, typical for MWCNT reported in previous studies [31]. The peak at 2h = 44 correspond to the iron catalyst present in the product. The weight percentage of Fe present in MWCNT was measured by thermo-gravimetric analysis and is shown in Fig. 1c. TGA also provides the information on the different types of carbon structures based on their reactivity toward air oxidation. All the MWCNT were oxidized to CO2 at around 600 C leaving behind only Fe particles which was estimated to be

2. Experimental 2.1. Materials and functionalization of MWCNT The gas atomized Al powder was used as the matrix with average particle size <25 lm and purity 99.0%. MWCNT used in the present work were synthesized in our laboratory using CVD [31] by the decomposition of toluene in the presence of iron catalyst. This catalyst was obtained by the decomposition of ferrocene. The central reaction zone was maintained constant at 750 C and the solution containing toluene and ferrocene was injected in the reactor where the temperature was $350 C. Ar was used charge as the carrier gas. Functionalization of MWCNT was carried out by ball milling in the presence of NH4HCO3. For this purpose, 3.20 g of NH4HCO3 was mixed with 0.50 g of MWCNT and sonicated in ethanol for 3 h followed by drying the mixture using a magnetic stirrer with constant stirring. The mixture was then put into a stainless steel container containing ZrO2 grinding balls of 10 mm diameter. The balls to powder weight ratio was 18:1. The container was rotated at a speed of 250 rpm and the milling was carried out for 24 h. The ball-milled sample was then heated under vacuum for about 24 h at 100 C to remove the residual gases. The amine and/or amide groups attached onto the surface of MWCNT were analyzed using Fourier transformed infrared (FTIR) spectroscopy. High-resolution transmission electron microscopy (HRTEM) was used to study the microstructure of Al-fCNT composites. The composite powder was dispersed by ultrasonication for

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Fig. 1. (a) SEM image and (b) XRD pattern (c) TGA and (d) HRTEM of pure MWCNT (e) FTIR spectrum of fCNT (f) Raman spectrum of (a) MWCNT and (b) fCNT.

10 wt.% by weight of MWCNT. The burning temperature is higher than 400 C, indicating nearly no amorphous carbon present in the product. It is worth noting that the amorphous carbon burns at temperatures below 400 C, which is much lower than the MWCNT decomposition temperature of around 500 C. The HRTEM image of MWCNT used in the present work is shown in Fig. 1d. Some Fe nanoparticles embedded inside the nanotubes are also

shown in this gure. Further, as Fe nanoparticles are embedded inside the nanotubes, they are believed not to take part in any chemical reaction with Al during the sintering process. These MWCNT were used for functionalization by ball milling in the presence of NH4HCO3. Fig. 1e shows FTIR spectra of the fCNT synthesized in the present work. From this gure it is clearly seen that the attachment of amine and amide groups onto the surface of MWCNT via

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covalent bonding and/or physical adsorption. The IR analysis showed the absorption peaks corresponding to CN stretching (1241, 1303, and 1340 cm1), N-H bending (1485 cm1), NH stretching (3346, 3516 cm1) and CONH (3696 cm1) are attached on the surface of carbon nanotubes. The peak at 724 cm1 could be due to out-of-plane NH2 bending mode. It is expected that during the ball milling NH4HCO3 is decomposed into NH3, CO2 and H2O. It also introduces some defects and break C-C bonds on the surface of carbon nanotubes [32,33]. It is likely that during the ball milling process the concentration of these defects increases and results in the formation of amorphous carbon [34]. These defects allow amine and amide groups to form covalent bonds with broken CC bonds on the surface of carbon nanotubes. Raman spectroscopy is a powerful nondestructive tool to characterize carbonaceous materials, particularly for distinguishing ordered and disordered crystal structures of carbon. The typical features for carbon in Raman spectra are the G band (graphite) around 1582 cm1 and the D band (defect) around 1350 cm1. The G band is usually assigned to the E2g phonons of C sp2 atoms, while the D band is a breathing mode of k-point phonons of A1g symmetry. Fig. 1f shows the Raman spectra of MWCNT and fCNT used in the present work. For MWCNTs the Raman peaks were observed at 1577 (G-band) and 1347 cm1 (Dband) and for fCNTs the peaks were observed at 1578 and 1344 cm1 for G- and D-band respectively [35]. Thus, no signicant shift in Raman peaks was observed for MWCNT and fCNT. The relative intensity between the two peaks is known to provide information about the quality of the internal CNT. From Fig. 1f, the ratios of the peak intensity between D- and G-bands, ID/IG, were calculated. The ID/IG ratio represents the defect density in graphitic structures. The value of ID/IG was found to be $0.33 for MWCNT and $0.43 for fCNT respectively. This means that although the amount of defects apparently increased in the MWCNT after high-energy ball milling, there was no signicant structural change in fCNT which was produced by the ball milling of MWCNT in the presence of ammonium bicarbonate. 3.2. Dispersion of fCNT in Al powder as a function of milling time The dispersion of fCNT in Al powder was studied using SEM. For this purpose, a mixture containing Al powder and 1.5 wt.% fCNT were ball milled in a stainless steel container lled with Ar gas at a pressure of about 300 kPa for different milling times. Fig. 2ae shows typical SEM micrographs of a mixture of Al powder and 1.5 wt.% fCNT milled for 5, 10 and 15 h respectively. SEM micrographs as shown in Fig. 2a, c, and e were taken at lower magnication showing the uniform distribution of fCNT in Al matrix and those shown in Fig. 2b, d, and f were taken at higher magnication showing the degradation of fCNT with increase in milling time. From this gure, it is clear that in a 5 h ball milled sample fCNT (Fig. 2a and b) were agglomerated in Al powder and have whiskers-like structures on the surface as also observed by Wang et al. [25]. Thus the fCNT were also not dispersed in Al powder after 5 h of ball milling. After 10 h of ball milling (Fig. 2c and d), the length of the fCNT were found to be relatively short and their concentration on the surface of Al powder also decreased. Eventually, after 15 h of ball milling most of the fCNT were found to be embedded in Al powder as observed in (Fig. 2e and f). Most of the tangledthread-like structures disappeared and only small end portions of fCNT were protruded from the Al surface. This phenomenon is observed by Wang et al. [25] after ball milling a mixture of Al and MWCNT for 72 h. However, it is clear that ball milling Al powder in the presence of fCNT certainly prevented the agglomeration of nanotubes as well as Al powder. The composite powders of Al and fCNT milled for 5, 10 and 15 h containing different weight percentage of fCNT were ultimately used for the fabrication of composites using PM route.

3.3. Microhardness and compressive strength measurements of the composites The microhardness of the composites fabricated in the present work by cold compaction at 550 MPa followed by sintering at 620 C under a vacuum of 102 torr for 2 h was measured at room temperature in accordance to ASTM standard E384 using a Zwick 3212 microhardness tester under a load of 200 g. Before measurements, the samples were polished well using a ne diamond paste in order to obtain a mirror like surface so that the indentation could be read very carefully. Also, the measurements were done at ten different points and the average value of hardness was taken. Although the hardness in pure metals is found to depend on the applied load, in case of composites no signicant change in microhardness was observed when the load was varied. For comparison, the microhardness of pure Al composites sintered under similar conditions was also measured. Some of the important results of this study are given in Table 1. From this table it is clearly seen that the average micro hardness of the composites loaded with 1.5 wt.% MWCNT increases from 31 to 52 10 kg/mm2. However, the micro hardness value was found to increase to 64 10 kg/mm2 when loaded with 1.5 wt.% fCNT. This increase in microhardness value was attributed to the better dispersion of fCNT in Al matrix as compared to MWCNT. Further, as ball milling was found to assist the dispersion of fCNT in Al matrix, it is seen that the composites made from ball milled mixtures showed further improvement in the micro hardness values. The results on the effect of ball milling on the average micro hardness shows that hardness value from 66 to 190 10 kg/mm2 when the milling time was increased from 0 to 15 h. This value is more than 3 times the hardness observed for pure Al composites and higher than the values of the composites (182.8 kg/mm2) prepared from non-functionalized (2 wt.%) MWCNT-Al mixture ball milled for 72 h [25]. These results conrmed the better dispersion of fCNT in Al matrix as compared to MWCNT and could be responsible for the improved hardness in Al-fCNT composites. It is also expected that the fCNT form a much stronger interfacial bonding between fCNT and Al matrix leading to the formation of a thin transition layer of Al4C3 under the sintering conditions. This transition layer may help in load transfer from the Al matrix to fCNT more effectively. In order to see the effect of fCNT concentration on the hardness of composites, the samples of Al and fCNT (0.53.0 wt.%) were ball milled for 510 h and then sintered at 620 C for 2 h under a vacuum of 102 torr. The results are shown in Fig. 3ac. From these results, it was found that the hardness of the composites increased with increasing the concentration of fCNT. From Fig. 3 it is seen that the micro hardness of pure Al composites fabricated from 10 h milled powder was found to decrease slightly than those fabricated from 5 h milled powder. This was mainly due to increase in particle size of pure Al with increase in milling time due to cold welding instead of cold working, thereby leading to decrease in hardness of the composites. The variation in micro hardness is clearer in samples milled for 10 h. According to our observations (Fig. 3b) it reaches a maximum (190 kg/mm2) for composites loaded with 1.5 wt.% fCNT, and then dropped with a further loading of fCNT. However, in a composite of Al-fCNT fabricated from a 15 h ball milled composite powder it was found that the average micro hardness increased to about 364 10 kg/mm2 when the fCNT loading was increased to 2 wt.%. At some places, the hardness values of 450 10 kg/mm2 was also observed, which is highest value of micro hardness for Al-fCNT composites reported so far to the best of our knowledge. It may be mentioned that the maximum value of hardness observed by Wang et al. [25] was only about 182.8 kg/mm2 after loading Al powder with 2 wt.% MWCNT and 72 h milling time. The maximum microhardness of composites obtained using 2 wt.% acid functionalized CNT was only 54 kg/mm2 [12]. These results also conrm the better dispersion of fCNT in Al

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Fig. 2. SEM micrographs of a mixture of Al powder and 1.5 wt.% fCNT milled for 5 (a and b) 10 (c and d) and 15 h (e and f). Figs. (a, c, and e) are at low and (b, d, and f) at higher magnication.

Table 1 Micro hardness of the composites under a load of 200 g. Material Pure Al composite Al + 1.5 wt.% MWCNT Al + 1.5 wt.% fCNT Pressure (MPa) 550 550 550 Temperature (C) 550 550 550 Average hardness (kg/mm2) 31 10 52 10 64 10

matrix as compared to MWCNT and acid functionalized CNT. The higher value of hardness in fCNT-Al composites fabricated in the present work could be explained by the formation of few hard phases of Al namely Al4C3, c-Al2O3 and AlN during the processing conditions. Al4C3 was formed mainly from the chemical reaction of amorphous carbon (present on the surface of fCNT) and Al powder during the sintering temperature of 620 C used in the present work. AlN nitride could be formed through the chemical reaction of amine groups attached on the surface of MWCNT with Al powder and c-Al2O3 by the reaction of Al with stearic acid as also observed by Kubota [23]. The formation of c-Al2O3 and Al4C3 was observed by Kubota [23] at a sintering temperature of about 500 C and higher. As the sintering temperature in the present work was mainly 620 C, it is expected that these phases were also formed in Al-fCNT composites during the sintering conditions and assisted in increase in hardness of these composites. At higher concentration of fCNT (3 wt.%) the micro hardness was found to decrease in all the composites synthesized from 5 to 15 h milled powder as shown in

Fig. 3. For example, the average hardness of composites fabricated form a 15 h milled powder was found to decrease from 364 to 123 kg/mm2 when the fCNT concentration was increased from 2.0 to 3.0 wt.%. The decrease in hardness with higher concentration of fCNT (3 wt.%) may be explained due to the reagglomeration of fCNT and relatively lower dispersion in Al matrix. From the results obtained in the present study it is concluded that the optimum concentration of fCNT in Al powder should not be higher than 2 wt.% in order to obtain composites with improved mechanical properties. The compressive strength of some of the composites fabricated in the present work was carried out at room temperature on a Universal testing machine in accordance with ASTM standard E9-09. For this purpose, rectangular specimens with 2:1 ratio of heightto-width were prepared for compression tests. The specimens were polished to make the surfaces totally at and were greased. Compression tests were conducted at a rate of 0.008 mm/s. Four specimens (size: height = 4 mm and width = 2 mm) were tested for each condition and the average value of compressive strength

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Fig. 3. Variation of Vickers micro-hardness with fCNT loadings in Al matrix composites. The samples were milled for (a) 5 h, b) 10 h and (c) 15 h.

is reported. A maximum value of 190 10 MPa was observed for Al composite loaded with 1.5 wt.% fCNT. However, not much change in the compressive strength was observed when the weight percentage of fCNT was either decreased to 1 wt.% or increased to 2 wt.% and the average compressive strength of these composites was found to be $186 20 MPa. The maximum compressive strength observed for an Al composite loaded with 0.5 wt.% MWCNT and fabricated using spark plasma sintering followed by hot extrusion was only 80100 MPa [36], which is much lower than the compressive strength of composites fabricated using fCNT in the present work. 3.4. X-ray diffraction (XRD) analysis of the composites In order to conrm the presence of and Al4C3, c-Al2O3 and AlN in the Al-fCNT composites fabricated in the present work at a pressure of 550 MPa followed by sintering at 620 C under a vacuum of 102 torr for 2 h, XRD analysis was carried out for these composites. Fig. 4ac shows typical XRD patterns of Al-fCNT composites fabricated from a 15 h milled mixture of Al powder loaded with 1 wt.%, 1.5 wt.% and 2 wt.% fCNT respectively. Several peaks corresponding to c-Al2O3, Al4C3 and AlN are indexed in Fig. 4ac. Although the overall concentration of Al4C3 in all the Al-fCNT composites fabricated in the present work was very low, it increases slightly with increase in fCNT concentration from 0.5% to 2.0% by

weight of Al. Such increase in the concentration of Al4C3 results in the increase in microhardness of the composites as shown in Fig. 3ac. However, in the XRD patterns shown in Fig. 4ac it is very difcult to detect such small increment because of the overall low concentration of Al4C3. At higher concentration of fCNTs (>2 wt.%), the agglomeration of the nanotubes is more pronounced and the overall mechanical properties of the composites are reduced. Although no amorphous carbon was detected on the walls or surface of carbon nanotubes used in the present work, a small amount may form during the ball milling experiments. However, this carbon is believed to form Al4C3 during the sintering conditions because of a relatively low free energy of formation (12.7 kcal at 298 K) [37]. In Fig. 4b no peak of c-Al2O3 was observed in the XRD pattern. It must be mentioned that in this sample the ball milling was carried out in the absence of stearic acid. Therefore, the peaks of c-Al2O3 as observed in Fig. 4a and c are mainly from the chemical reaction of stearic acid (C17H35COOH) with Al powder during the sintering conditions. 3.5. Microstructure and interfacial bonding of the interface The microstructure of the fractured surface of Al-fCNT composites after tensile testing was studied using SEM. Fig. 5 (a-c) shows the SEM micrographs of the fractured surface of a composite

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Fig. 4. XRD patterns of Al composites loaded with (a) 1 wt.% (b) 1.5 wt.% and (c) 2 wt.% fCNT respectively and sintered at 620 C.

fabricated by the cold compaction of a mixture of Al powder loaded with 1.5 wt.% fCNT (milled for 15 h) at 550 MPa followed by sintering at 620 C under a vacuum of 102 torr for 2 h. Fig. 5a and b shows SEM images of the fractured surface recorded at lower magnication and Fig. 5c recorded at higher magnication shows few pull out CNT from the fractured surface of Al-fCNT composite and are shown by white arrows. Also the average length of the pulled out fCNT was found to be about 100150 nm which is much smaller than the length of fCNT used initially (15002000 nm). This means that most of the fCNT are embedded in Al matrix, therefore, giving a higher bonding energy and hence higher strength in composites. Thus, we believe that the interfacial bonding between Al matrix and fCNT in the composites fabricated in the present study is also very strong. In order to understand the interfacial bonding between Al matrix and fCNT, the microstructure of the composites fabricated in the present work was further investigated by HRTEM. Fig. 6ac shows the HRTEM images of well formed grains of Al composite fabricated using 1.5 wt.% fCNT. Fig. 6a shows different grains boundaries of the sintered composite powder (black arrows). Fig. 6b and c shows HRTEM image of the composite with clear lattice images of Al, Al2O3 and Al4C3 components. At few places we found nanotubes at the edges of Al grains which are magnied in Fig. 6b. The microstructural details of all the phases of the microstructures present in the Al-fCNT were reconstructed using FFT to enhance the detailed micropattern. The analysis of the micrographs depicts that the well dispersed fCNT are well graphitized multiwalled nanotubes. The graphitic walls of the fCNT are apparent and the interlayer spacing between the sheets is 0.34 nm as observed by XRD also (Fig. 1b). Despite the curling of the carbon nanotubes at few places, as shown in Fig 6c (highlighted with curved lines), they show structural integrity & perfect walls. In the present work the Al matrix is reinforced with fCNT rather than graphite and hence we only have the carbide formation at the AlfCNT interface due to the absence of prism planes in CNT. The formation of the carbide nanoparticles have been reported only along the reactive prism plane in the graphitic structures and they are absent in CNT [19]. Few researchers have noticed the growth of carbide particles at the tip of the CNT in presence of the reactive prism planes in the graphite structure due to partially graphitized

Fig. 5. SEM images of the fractured surface of a composite loaded with 1.5 wt.% fCNT at different magnication.

CNT [38]. In our case due to the presence of defects in the walls (during ball milling) as well as the presence of amorphous carbon on the walls of CNT, some prism planes might be present to facilitate the growth of Al4C3 structures which appear in the form of transition layer between Al and fCNT of about 23 nm thickness (marked by white arrows in Fig. 6c). Also, because of the low free energy of formation, Al4C3 is easily formed from the reaction of amorphous carbon and Al at the sintering conditions. From the lattice parameters analyzed from the reconstructed lattice image as well as SAED pattern, it is clear that the layer is composed of Al4C3. The reconstructed pattern of the interlayer showing the cross lattice with lattice spacing of 0.28 nm and 0.21 nm corresponding to (0 1 2) and (0 0 1 2) planes of Al4C3 is elucidate in the rst reconstructed pattern and the lattice spacing of 0.4 nm corresponding to (0 0 6) plane is shown in the second reconstructed image of the highlighted regions. The third reconstructed image shows the clear presence of Al (2 0 0 plane). Thus the fCNT are well dispersed in Al powder and do appear to have an interfacial bonding. Besides the presence of Al, CNT and Al4C3, we also observed the presence of AlN and abundance of Al2O3 phases. This may be due to the surface reaction of amino groups attached on carbon nanotubes with aluminum powder and presence of free surface of highly reactive Al. A large increase in the hardness of the composites fabricated in this work is mainly due to the presence of thin transition layers of Al4C3 at almost every interfacial region of Al and CNT (marked by white arrows), as is clear in every high reso-

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Fig. 6. Representative HRTEM images of Al-fCNT composite synthesized from a 1.5 wt.% loading of fCNT and sintered at 620 C a) different grains boundaries of the sintered composite powder (arrow marked), b, & c) composite with highlighted area showing the presence of Al, AlN, Al2O3 and CNT. The reconstructed Fast Fourier Transformation (FFT) image of marked area shows the phases of Al and the interfacial bonding due to the formation of a transition layer of Al4C3 (marked with white arrows).

lution image which is also responsible for the strong interfacial bonding between Al matrix and fCNT. We would like to add here that due to milling also there can be occasional damage to the structure of the CNT resulting in change of the interlayer distance of the walls in addition to this there can be inltration of aluminum atoms in and out of the walls while milling for long duration resulting in the formation of few atomic Al nanostructures and hence the interlayer spacing of the CNT walls at few places is enlarged to 0.370.39 nm (marked with dotted arrow), but the overall structure is not damaged as also conrmed by Raman spectroscopy analysis of fCNT shown in Fig. 1f. Almost similar results on the inltration of Al atoms in and out of MWCNT during the ball milling experiments were reported by Choi et al. [18]. 3.6. Strengthening mechanism It is worth discussing that the homogeneous dispersion of fCNT in Al matrix has a resemblance with dispersion-strengthened Al alloys, where in the latter case the intermetallics formed during synthesis have improved mechanical strength stable at elevated temperatures. In the strengthening mechanism operating in Al-fCNT composites, a number of factors should be considered e.g. the wetting of fCNT and Al matrix, thermal mismatch and the formation of a thin transition layer between fCNT and Al

matrix. The wettability of MWCNT in Al was found to be very low due to their large difference in surface energies [37]. However, with the formation of Al4C3 at the Al-MWCNT interface, the wetting surface for liquid Al changes to Al4C3 and the wetting angle decreases from 135 to 140 (which is typical of non-reactive metalgraphite system) to $55 [39,40]. Thus, the adhesion between the Al and fCNT in the present case also can be interpreted in terms of strong chemical interactions, such as covalent bond. Although, there is a large thermal mismatch between MWCNT and Al the volume contraction of Al at the sintering conditions may contribute to the mechanical adhesion of the MWCNT to the Al matrix [41]. In the present case because of the presence of amine and amide groups on MWCNT the adhesion of fCNT to the Al matrix is even better. The other key factor for the stress transfer from Al matrix to the fCNT is the formation of an intermediate transition layer between the fCNT and Al matrix. The HRTEM results as shown in Fig. 6 shows that this transition layer was found to be of Al4C3. This transition layer was mainly formed from the reaction of amorphous carbon (present either on the surface of fCNT or due to structural defects present in fCNT (during ball milling) and Al at the sintering conditions because of a relatively low free energy of formation, although no signicant structural changes were observed in fCNT (Fig. 1f). The formation of this transition layer is also believed to increase the interfacial bonding between fCNT and Al matrix [38]. The nanoscale reaction product, Al4C3, which has a tight

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contact with the surface of fCNT, and is physically harder than Al phase, can stop the slippage of fCNT away from the Al. The size of the Al4C3, is limited due to the small supply of amorphous carbon. In the present case the thickness of this transition layer was found to be $23 nm as conformed by HR-TEM results (Fig. 6). The carbide formation on the surface of fCNT improves the interfacial interaction between the fCNT and Al layers and thus contributes to the overall enhancement of mechanical properties of the composites. The formation of nanosized strong interface of Al4C3 in Al-fCNT composites (Fig. 6) will also prevent delamination and thus improves the stress transfer efciency. The slippage of the fCNT from the Al- matrix is probably stopped mainly due to the fact that the nanotubes are wrapped around various grains-which make it difcult for pullout. Finally, the hardness of MWCNT being comparable to diamond would lead to a strong interface between Al and the surface of fCNT, and, this in turn cause constraints to mechanical shocks and deformation. The SEM and HRTEM images of the composites fabricated in the present work showed that the fCNT in the composites are intact without any signicant distortion during their processing. 4. Conclusions Al composites were fabricated using the powder metallurgy process in which fCNT were used as the reinforcement material and the sintering was carried out between 550 and 620 C. The mechanical properties of these composites were found to be superior to those prepared using MWCNT loadings under similar processing conditions. The large increase in the micro hardness of the synthesized Al-fCNT composites is mainly due to the formation of few phases of Al such as AlN, Al2O3 and Al4C3 having higher densities than Al during the sintering process. The higher dispersion of fCNT in Al matrix and formation of a strong interfacial transition layer of Al4C3 along the fCNT is mainly responsible for the increase in strength in these composites and improved stress transfer from the Al matrix to the fCNT. For practical applications, the fabrication temperature of Al-fCNT composites should be kept below the Al melting point. From this point of view, the PM process is most likely the technique of choice to fabricate the best Al-fCNT composites. Acknowledgements The authors are grateful to the Director, NPL, New Delhi for his permission to publish the results. Sincere thanks are due to Mr. R.K. Seth, Mr. K.N. Sood, Ms Arpita Vajpayee and Dr. Shailesh Sharma for their help in TGA, SEM, XRD and FT-IR characterization. References
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