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Growth of carbon nanotubes above the peritectic temperature of tungsten metal catalyst
D. Harbec *, J.-L. Meunier
Department of Chemical Engineering, McGill University, Montreal, QC, Canada

A R T I C L E I N F O

A B S T R A C T

Article history: Received 10 September 2010 Accepted 21 January 2011 Available online 26 January 2011

The mechanism of formation of carbon nanotubes (CNTs) produced from the dissociation of tetrachloroethylene (TCE) and the co-injection of tungsten vapour in the nozzle of a DC thermal plasma torch is discussed. Tungsten and the dissociation of TCE form nanoparticles of tungsten carbide (WC), which provide the catalyst activity for the formation of CNTs. A new route for the mechanisms of formation is discussed following thermodynamic equilibrium calculations of the plasma torch system, energy dispersive spectroscopy and nanodiffraction analyses of the WC nanoparticles formed. These analyses provide an understanding of the dissociation pattern of TCE, evaluate the carbon concentration in the catalyst nanoparticles and determine the phase structure of these nanoparticles. We propose from these results a new mechanism of formation for CNT occurring above the peritectic temperature of the stoichiometric WC alloy. Crown Copyright 2011 Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Carbon nanotubes (CNTs) are long hollow tubes made of carbon uniquely and are characterized by their nanometric diameter and their micron-size length, giving them a onedimensional structure. They feature a high modulus of elasticity, a high tensile strain, superconductor and semiconductor behaviours, a high thermal conductivity, the possibility for gas storage and applications linked to their very large specic area. Novel promising applications are now being developed in advanced materials such as high strength materials [1,2], in high conductivity nanouids [3,4], electronic components such as transistors [5], electron emitters [6], fuel cell electrodes [7,8], and energy storage [9,10]. The availability and the high cost of CNTs however still limit the development and the commercialization of many applications. The road towards industrial processes for the growth of CNTs involves an understanding of the mechanism of formation at the nanoscale and of the fundamental phenomena at the basis of this formation.

In the late nineties, researchers noticed that the introduction of a metal catalyst in CNT synthesis methods enhance the yields [11]. For instance, doping the graphite anode with some specic metal in the arc discharge method not only produces CNT in the deposit on the cathode, but enables the condensation of CNT on the walls of the arc chamber [1215]. Metal catalysts enhance the yields of CNT by anchoring the edge of the CNT structure. These mainly inhibit the formation of pentagonal rings preventing a premature closure of the CNT structure into by-products, and allow an efcient elongation and growth of the CNT. Researchers rst thought that the metal catalysts in their elemental state acted as a transitional element permitting the addition of the carbon building blocks at the tip of the CNT structure [16,17]. Later, Zhang et al. [18] suggested that the metal catalyst in the form of nanoparticles encapsulates the tip of the CNT structure allowing an efcient growth and preventing a premature closure of the tube structure. At the present time it is rather proposed that CNTs grow rst from a diffusion process of elemental carbon into the

de Sherbrooke, Sherbrooke, QC, Canada. * Corresponding author: Current address: LMCA/Department of Civil Engineering, Universite Fax: +1 819 821 7212. E-mail address: david.harbec@usherbrooke.ca (D. Harbec). 0008-6223/$ - see front matter Crown Copyright 2011 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2011.01.050

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metal catalyst particles having a diameter in the nanometer scale. Authors [1926] indicated that the growth of CNT passes rst through the nucleation of carbon clusters and metal nanoparticles at high temperature. The metal nanoparticles dissolve the carbon clusters forming a metalcarbon mixture. At some proper temperature for the phase separation of the metalcarbon solid solution, the particle segregates a fraction of its carbon which graphitizes and forms CNTs at the surface of the particle. The nanometer size range of the particle is an essential condition for generating the tubular structures. In fact even for the growth of CNT directly on at metal surfaces using CVD techniques, a prior surface treatment generating nano-scale defects of the metal surface is essential for the formation of this structure [27]. Once extraction from the catalyst site is triggered, the growing CNT continuously uses the segregated carbon as building blocks to elongate their structure [1926]. Carbon in the gas phase may also be used in the growth of CNTs, this however is expected to occur through a surface diffusion process on the tubular structure eventually feeding the metal solution in carbon [19]. During the segregation process, the key parameter for high yields of CNT is the control of the eutectic temperature for phase separation of the metalcarbon mixture. Kataura et al. [20] proposed a growth mechanism composed of three steps, where the rst step occurs at high temperature, the second, at medium temperature and the third, at low temperature. In the rst step, the dissociation of both the carbon raw material and metal catalyst at high temperature leads to the nucleation of fullerene caps, carbon clusters and metal nanoparticles. The metal nanoparticles attract fullerene caps on their surface and dissolve some of the carbon clusters, forming a metalcarbon mixture. At the medium temperature state in step two, the metalcarbon mixture stops dissolving carbon clusters and attracting fullerene caps on its surface. In step three, another quench occurs and the solubility of carbon in the metal reduces signicantly. The metalcarbon mixture segregates the excess of carbon and fullerene caps elongate their structure into CNTs using the segregated carbon. Here, the diameter of the fullerene caps determines the diameter distribution of the CNTs. These authors noticed that the temperature inuences the elongation process of CNT in step three. Controlling the temperature below the eutectic deactivates the elongation process and shortens the resulting CNT. A temperature near the eutectic strongly activates the growth of CNT. Nasibulin et al. [21] and Brukh and Mitra [22] worked on reaction pathways of the decomposition of the carbon source yielding the presence of free carbon. Their modeling calculations and experimental data demonstrate a correlation between high availability of free carbon and high yield of CNTs. They indicated that a high concentration of free carbon improves the initial diffusion step in the metal catalyst nanoparticles. Larouche et al. [23] suggested that instead of the elongation of fullerene caps as described above, their mechanism of formation rather passes through the extrusion of CNT cords from the metalcarbon mixture induced by the Marangoni convective process in the liquid layer at the surface of the particle. For achieving high yields of SWNT in their plasmabased gas phase synthesis, the quench of the iron nanoparti-

cle precursors must occur at a fast rate of at least 106 K/s in order to generate the nanometer size structure. Following the metal nanoparticle generation stage, a lower temperature in the range of the eutectic temperature of the particle is maintained for the catalyst, leading to carbon extraction and growth of CNTs. The importance of the eutectic transformation and of a good control over the specic eutectic temperature range for the nanoparticle was further conrmed in many studies (see for example [28,29]). In situ and real time conrmation of this growth process within a transmission electron microscope was even obtained by Rodriguez-Manzo et al. [30], with the added information of a gradual change of the Fe nanoparticle structure from the carbon-rich zone in the region of tube formation, to the carbide phase forming away from this zone following carbon depletion. The importance of controlling a very specic temperature for the eutectic phase transformation, along with the need for the nanoscale catalyst structure, is responsible of the main difculties for the generation of CNT. In the present paper, we discuss a system which generates CNTs even though it does not have a eutectic transformation capable of extracting carbon. We show that another route for carbon extraction is possible and that, contrary to the eutectic transformation, this transformation involves a continuous cooling of the liquid metalcarbon system over a very wide temperature window enabling easier control over the process. In a previous work, we showed the catalytic production of CNTs using tetrachloroethylene (C2Cl4, TCE) as the carbon raw material injected in the nozzle of a DC thermal plasma torch. The erosion of the DC torch electrode, made of tungsten, emits metallic vapours that nucleate in situ into catalytic nanoparticles within the plasma jet [3134]. The advantage of using the technology of thermal plasma torch is their scale-up capability, because of their high throughput and high power availability. One should note that plasma torch systems are currently being used industrially at the megawatt power scale. Moreover, such system enables decoupling of the catalyst nucleation zone from the CNT growth zone and an independent control of the process parameters: power, carbon source and metal catalyst feeds. The present paper provides results on the mechanism of formation of the CNTs within the torch nozzle using these particular tungsten/TCE precursors. This mechanism of formation evolves rst from thermodynamic equilibrium calculations for an understanding of the TCE dissociation in the plasma torch, from electron microscopy observations and analyses for evaluating the carbon concentration in the catalyst nanoparticles and determination of the phase structure of these nanoparticles. The mechanism of formation is observed here to occur above the peritectic temperature of the WC mixture.

2.

Experimental

As previously outlined [3134], we inject TCE vapours at a rate of 0.050.29 mol/min using 20 slpm of argon carrying gas in the water-cooled nozzle of a DC non-transferred thermal plasma torch, operated with 100 slpm of plasma-forming argon and a torch power of 30 kW. Upstream of the torch nozzle,

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the arc plasma erodes the anode and the cathode both made of tungsten and supplies a small amount of tungsten vapour as a source to nucleate the liquid catalyst nanoparticles in the large quench provided by the supersonic expansion in the torch nozzle. The very high temperatures above 4000 K in the nozzle zone downstream of the expansion are expected to maintain the tungsten nanoparticles in the liquid state. The dissociation of TCE in the nozzle provides atomic carbon contamination to the nucleated tungsten particles, forming nanoparticles of tungsten with carbon in solution. TCE was selected as the carbon precursor because of the complete dissociation of the CCl bonds and the generation of free C species in the temperature range of interest (see Section 3). The tungstencarbon solution nanoparticles having suitable temperature and size represent the site for CNT growth. A large fraction of these nanoparticles are transported radially in the torch nozzle by thermophoresis, and attach to the nozzle wall. These particles are characterized by having very long residence times in a given high temperature window, together with a continuous supply of atomic carbon. Such a situation leads to the observed long CNTs, mainly MWCNT, showing average lengths exceeding 50 lm [31,34]. We characterize CNTs and the catalyst nanoparticles using High Resolution Transmission Electron Microscopy (HRTEM: Jeol JEM 2100F). The HRTEM is operated using 200 kV of accelerating voltage. The CNT samples are deposited on a copper mesh observation grid coated with an amorphous carbon lm. The magnication during the soot observation varies from 100 to 1000 k times. To characterize the catalyst nanoparticles, the elemental component are identied and quantied using Energy Dispersion Spectroscopy (EDS) from Oxford Instrument, and their phase structure is determined by nanodiffraction techniques.

erosion measurements for the plasma torch operating with 100 slpm of plasma-forming argon at 30 kW. We base our calculations on one mole of chemical species. Fig. 1 represents the calculated equilibrium molar fraction of the different possible chemical species from the dissociation of TCE and the addition of tungsten vapours for the 2739000 K temperature range. The upper temperature limit corresponds roughly to the modeled temperature of the plasma jet entering the nozzle region, which under the present conditions was evaluated in the range between 9000 and 9500 K [35]. The thermodynamic analysis here predicts that the use of a chlorinated carbon precursor, TCE in this case, for the formation of CNTs leads to the formation of large amounts of graphite and of relatively low amounts of chlorinated carbon products in the range of temperatures of interest (800 3000 K). In fact, we observe a complete break up of the CCl bonds at 800 K. Around 2990 K, the eutectic and the peritectic points of WC [36], most of the carbon and chlorine present are, respectively in the form of the graphitic structure and mono-atomic chlorine gas (Cl(g)). At high temperature (above 3000 K), dissociation of TCE and the erosion of the tungsten electrodes favour the formation of free gaseous C species: C(g), C2(g) and C3(g). Species containing CCl bonds are not predicted to be stable in this temperature range. Given the high temperature of the plasma jet and the relatively long residence time of the tungsten carbide particles deposited on the nozzle wall [33,34], one may speculate that free carbon species produced at high temperature diffuses into the W nanoparticles to form nanoparticles made of a WC solid solution or some WxCy compound.

4. HRTEM and EDS analysis of the catalyst nanoparticles

We previously reported that the ow and the temperature conditions within the torch nozzle enable a good dispersion of tungsten and the synthesis of large concentrations of 50 lm long MWCNT and carbon nano-onions [31,33,34]. Using TEM, these MWCNT are typically of several lm long and their internal and external diameters are, respectively, 23 and 1020 nm. TEM micrographs (Fig. 2) show nanoparticles of tungsten carbide encapsulated at the tip of CNT and in nano-onions. The typical size of these particles varies between 20 and 30 nm. In order to investigate if the growth of CNT is controlled by the segregation of the excess of carbon contained in the nanoparticles of metal catalyst, we evaluated by EDS and HRTEM the concentrations of carbon and tungsten within the catalyst nanoparticles encapsulated at the tip of a CNT. For comparison purposes, we rst analyzed the nanoparticles encapsulated in an early closed MWCNT made of concentric graphitic layers similar to nano-onions. We then compared this analysis with that of the catalyst particles located at the tip of a long MWCNT that extends as a full tubular structure. Fig. 3a and b, respectively represent the EDS analysis and the HRTEM micrograph of the catalyst region of an encapsulated tungsten carbide particle and of a long MWCNT. Care was taken to limit the EDS analysis to the metal nanoparticle

3.

Thermodynamic analysis

We perform the thermodynamic equilibrium calculations using the operating conditions yielding high concentrations of CNTs in an attempt to understand the dissociation pattern of TCE at high temperatures. This analysis is based on the method of the minimization of the Gibbs free energy. These calculations are made using the equilibrium computational program Ivtanthermo (CRC Press, 1993). There are however a few cautions in using such analysis. In thermal plasma chemistry, the residence times of the different chemical species are short, especially in the supersonic expansion within the torch nozzle. Equilibrium calculations are thus insufcient for predicting the exact composition of the products. Furthermore, these calculations do not take into account any kinetic factors that may possibly inuence the formation of certain compounds. As a result, the calculations in this work serve only as a guide to understand the chemistry behind the dissociation of TCE at high temperatures, rather than providing an accurate prediction of the product concentration. The following operating conditions are used in the equilibrium evaluation: plasma-forming gas: 100 slpm of argon, TCE feed rate: 0.15 mol/min, tungsten electrodes erosion rate: 4.3 103 mg/s [31,34] and reactor pressure: 0.26 atm. The amount of tungsten vapour is estimated from the electrode

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(a) 1.40E-01
Cl(g)

1.20E-01 1.00E-01

Mole

8.00E-02
Cl2 (g) Graphite C(g)

6.00E-02 4.00E-02 2.00E-02 0.00E+00 0 1000 2000 3000 4000 5000 6000 Temperature (K) 7000 8000 9000
CCl4 (g) C3 (g) C2 (g) C+(g) Cl+(g)

(b) 3.50E-07
WCl6 (g) WCl4 (g) W+(g) WCl6 (s) W(g) WCl (g)

3.00E-07 2.50E-07

Mole

2.00E-07 1.50E-07
WCl3 (g)

1.00E-07
WCl5 (g)

5.00E-08 0.00E+00 0 1000 2000 3000 4000 5000 6000 Temperature (K) 7000 8000 9000

Fig. 1 Computed mole fraction at equilibrium for the different chemical species resulting from the dissociation of 0.15 mol/ min of TCE and the addition of 4.3 103 mg/s of W vapours coming from the erosion of the torch cathode at 0.26 atm: (a) carbon and chlorine species; and (b) species related to tungsten.

on both observed structures with the surrounding layers of carbon remaining outside of the beam in order to isolate as much as possible the nanoparticle itself. The copper lines in the spectra are attributed to the meshes of the HRTEM observation grid. The nano-onion structure around the encapsulated tungsten carbide particle in Fig. 3b consists of 14 layers of graphitized carbon that encapsulate a nanoparticle of tungsten carbide of roughly 20 nm in diameter. In Fig. 3b, this structure is treated with an inverted Fast Fourier Transform to highlight the graphitized layers from the superimposed MWCNT. This structure is superposed in the gure over a long MWCNT also having 14 layers. The presence of encapsulated tungsten carbide particles in the nozzle deposit is presumably due to a short residence time of the nanoparticle in the appropriate temperature zone for CNT synthesis. In Fig. 4, a long MWCNT is seen to have grown using a catalyst nanoparticle of tungsten carbide of similar diameter (20 nm). A different number of layers of graphitic carbon is observed between the region directly around the nanoparticle

and that of the main tubular structure. The MWCNT possesses nine layers around the catalyst nanoparticle, and 14 concentric layers in the main tube structure. One can see the additional layers on the main tube structure are located inside the tube and attach directly to the catalyst particle, these sites acting as carbon extraction zones. We can also observe that the tungsten particle region away from this carbon extraction zone shows aligned crystalline planes, while the zone of carbon extraction is depleted from any organized crystal plane arrangement. This behaviour is similar to the structures observed on iron by Rodriguez-Manzo et al. [30]. Table 1 compares the relative concentrations of carbon in the metallic nanoparticles for both cases. The calculations of these concentrations are based on the intensity ratio of the tungsten and carbon lines on the EDS spectra. As stated earlier, the electron beam for the EDS analysis is focused within an area of 20 nm in diameter bounded by the nanoparticles of tungsten carbide. The carbon from the layer around the nanoparticle is not taken into account in the calculations. Besides the carbon contained within the nano-

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ter-layer spacing of the atomic planes [33,34]. As for the EDS analyses in Section 4, the electron beam of the HRTEM is directly projected on the catalyst nanoparticle encapsulated at the tip of a long MWCNT (Fig. 4b), while leaving the external layers of carbon outside of the beam. The measured inter-planar distances evaluated from the electron diffraction patterns are 1.30, 1.31, 1.46 and 2.5 A [33,34]. These four inter-planar values commonly represent the structure of the d phase in the WC system, which corresponds to the stoichiometric tungsten carbide (WC) phase [JCPDS File 51-0939]. The nano-diffraction pattern thus indicates that CNT growth generates nanoparticles of stoichiometric WC, while the zone showing an amorphous-like structures in the TEM gures may possibly be a solid solutions of tungsten with a high concentration of carbon. This type of structure agrees with high concentrations of carbon in the particles. In the phase diagram of the WC system (Fig. 5), stoichiometric WC (d phase) is effectively generated upon cooling within the high carbon concentration range (50 at.% C to <100 at.% C). In this range, no other form of the solid WC system is found besides the d and graphite phases.

6.
Fig. 2 Nanoparticles of tungsten carbide encapsulated at the tip of CNTs and in nano-onions.

Discussion and mechanism of formation

particle, the electron beam integrates the carbon observed above and underneath the nanoparticles. In order to estimate the concentration of carbon in the catalyst nanoparticles, some further calculations are needed to exclude these extra layers of carbon from the raw concentrations data. These calculations use the following assumptions: 1. The contribution from the TEM carbon support in the concentration of carbon is the same for both cases. 2. The extra layers are graphene sheets composed only of . hexagonal rings and having a CC bond distance of 1.41 A 3. The catalyst nanoparticles have a spherical shape. 4. The analyzed structures are uniform in each direction with regards to their amount of carbon layers. 5. The density of the catalyst nanoparticles is the one of tungsten carbide and it is independent of the concentration of carbon.

5. Phase determination nanoparticles

of

the

catalyst

The results in Table 1 indicate very high concentrations of carbon in the catalyst nanoparticles in both cases of the carbon nanostructure. These may easily be biased towards high carbon content by the measurement technique, however to verify if such high concentrations of carbon are feasible and in agreement with the phase diagram of the WC system, exhibited in Fig. 5, we evaluated the phase structure of the catalyst nanoparticles using electron diffraction and measured the in-

The results in Table 1 indicates that the catalyst nanoparticles contain a high concentration of carbon for the case of the nano-onion (Fig. 3b), and a slightly reduced concentration of carbon for the case of the long MWCNT (Fig. 4b). These values are still believed to be biased towards high concentrations of carbon, since the amorphous carbon lm of the observation grid may be contaminating the results. We may however assume that the contribution of the carbon lm in the concentration of carbon is similar in both cases. We can hence draw some conclusions from the relative evolution of these results. We see a higher carbon concentration for a shorter or early growth stage, and respectively a lower concentration after a long growth stage. Such evolution agrees with a model of MWCNTs growing in part from the segregation of the excess of carbon contained in the nanoparticles of metal catalyst, as discussed by many authors (see for example Kataura et al. [20], Larouche et al. [23], Rodriguez-Manzo et al. [30]). In Fig. 5, the phase diagram of the WC system [36] indicates a rst eutectic point at a composition of roughly 22 at.% C and at a temperature of 2715 C. However, this rst eutectic point does not segregate the graphite structure expected for the growth of CNTs. It rather produces the a phase of pure W and the b phase of tungsten carbide with a composition of 32 at.% C. This b phase is stable down to 1250 C, at which temperature it transforms into the pure a phase of W and the d phase, being the stoichiometric WC. Two other eutectic points exist on the phase diagram: one close to 35.5 at.% C and the other at 41 at.% C. As for the rst case, these two eutectic points do not lead to the segregation of the graphite structure needed for the growth of CNTs. They lead to the nucleation of the b, d and c phases of WC. The conditions of thermal gradients and of carbon concentrations lead to a strong growth of CNTs within the plasma

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Fig. 3 (a) EDS analysis of a nanoparticle of tungsten carbide encapsulated particle in a nano-onion. (b) TEM micrograph of the encapsulated tungsten carbide particle superposed over a long CNT. Scale bar: 20 nm.

torch nozzle deposit at high temperature [3134]. The EDS analyses indicate concentrations of carbon in the nanoparticles that may be well above the stoichiometric CW phase. According to the CW phase diagram of Fig. 5, very high concentrations of carbon are necessary in a high temperature liquid tungsten system to enable the formation of the stoichiometric d phase of WC, and of the graphite phase that can be assimilated to the growth of CNTs. The temperature expected in the nozzle deposit, modeled by Guo [35] and cited in [33], takes into account the supersonic ow and the TCE reaction paths for evaluating the ow/energy elds. Results indicated temperatures well above 3000 K in this zone, down to temperatures of roughly 2000 K close to the nozzle wall.

This indicates the nucleated tungsten particles are effectively in the liquid state throughout most of their residence time on the nozzle wall deposit, a period corresponding to the availability of atomic carbon in the gas phase which is eventually loading the liquid droplets through diffusion. It is important to note that the d phase nucleation observed here is not a eutectic transformation, but a peritectic transformation occurring above 2785 C of the L + graphite two-phase domain. Looking more closely at the phase evolution in the phase diagram for concentrations above 50 at.% C, we propose here a new and simple mechanism for the nucleation and the growth of CNTs from catalysts having a peritectic transformation with carbon. This mechanism follows directly from the

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Fig. 4 (a) EDS analysis of a nanoparticle of tungsten carbide encapsulated at the tip of a long MWCNT. (b) TEM micrograph of the long MWCNT analyzed. Scale bar: 20 nm.

Table 1 Calculated concentrations of the different elements within the area bounded by the nanoparticle of metal catalyst. Elements in the nanoparticle Carbon Tungsten Nano-onion (at.%) 99.19 0.81 Long MWCNT (at.%) 91.91 8.09

transformations occurring upon cooling within the liquid + graphite two-phase domain at temperatures above the peritectic temperature. The sketch of Fig. 6 anticipates this evolution within the phase diagram above 50 at.% C upon cooling down in the 27853500 C range. Note the temperature

values indicated here do not take into consideration the reduction in transition temperature imposed by the nanometer scale of the particles. Upon the initial homogeneous nucleation of the W particle from the hot plasma in the supersonic shock zone, we expect

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Fig. 5 Phase diagram of tungsten carbide.

Fig. 6 Sketch of the evolution upon cooling within the phase diagram of tungsten carbide for carbon concentration above 50 at.%, and resulting in the formation of the d phase of stoichiometric WC and CNT.

this initial particle to be relatively pure of tungsten and to be in the state of a liquid droplet because of the high temperature in the torch nozzle. The liquid W particle is then driven towards the nozzle wall within the layer of deposit observed experimentally. During this transit, and even more during the period of residence in the nozzle wall deposit, its size is expected to increase from coagulation processes. Its concentration in carbon during this period should also strongly increase. When cooling within the liquid + graphite domain at

some overall particle concentration Co in Fig. 5, the concentration of carbon in the liquid is decreasing along the liquidus line in favour of an increasing amount of solid graphite-like structure being nucleated at a rate according to the lever rule evolution upon cooling. The thermal evolution of a liquid WC system in this two-phase region effectively produces the graphitic structure expected for the growth of CNTs. Contrary to the eutectic transformation, this process occurs along very wide ranges of both the temperature and the

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carbon concentration in the catalyst particle. It stops upon crossing the peritectic temperature value of the system. The WC liquid particle then solidies into the stoichiometric solid d phase of WC. Similarly to the eutectic transformation, the evolution of the graphitic structure from the particle is based on the liquid phase of the particle and the change of concentration upon the solidication of this liquid phase. The main difference comes from the decreasing concentration of carbon in the liquid phase upon cooling which forces, through the relative amounts of liquid and solid phases present, the growth of graphitic structures over the large temperature range. One can also note that an increase of the carbon concentration in the liquid particle will enhance this process. Such increase effectively leads to a greater proportion of graphite at some temperature in the L + graphite domain and to a larger temperature range for the growth of CNTs. This agrees well with the increase of the CNT concentration with the TCE feed rate explained in [32,33]. The efciency of this mechanism of formation of CNTs is expected to be quite high because of the large temperature range (27853500 C) and the large carbon concentration within the catalyst particle (50% to near 100%). This seems to correlate well with the very long CNTs exceeding 50 lm produced in the torch nozzle [31,34]. This mechanism is however possible only at temperatures higher than the peritectic temperature. This explains why no or very few CNTs are grown in the soot downstream of the torch nozzle and in the nozzle deposit during the rst 3 min of operation seen in [33,34]. A nal note should be made on the implications this peritectic route has on the processing aspects of CNT synthesis. The eutectic route involves maintaining a very narrow temperature window which is difcult to target and maintain, particularly in gas phase synthesis involving a priori the nucleation of metal catalyst nanoparticles using a strong quenching rate. The peritectic route described here on the contrary involves a slow cooling of the nanoparticles down a very large temperature domain that should be much easier to control downstream of a gas phase ow system.

50 lm observed in the torch nozzle [31,34]. Based on this mechanism of formation, the yield of CNTs is anticipated to increase following an increase of the carbon concentration in the particle. This anticipation agrees with the increase of the yield of CNTs with the increase of TCE feed rate described in [33,34]. Such mechanism of formation can possibly be applied to more usual metal catalyst systems for the growth of CNT. In fact, the ironcarbon and other similar systems are expected from the above analysis to show a similar growth behaviour when loaded in their liquid state with concentrations of carbon that are well above their eutectic composition value.

Acknowledgement
This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada.

R E F E R E N C E S

7.

Conclusions

In summary, experimental observations on CNTs generated in a high temperature plasma jet using a tungsten catalyst precursor enables the proposition of a new mechanism for the nucleation and the growth of CNTs from the catalyst nanoparticles in this case. This mechanism follows from the cooling within the liquid + graphite two-phase domain of the WC phase diagram at temperatures above the peritectic temperature of 2785 C. When cooling within the liquid + graphite domain at high carbon concentrations, the thermal evolution of a liquid WC solution particle in the two-phase region produces the graphitic structure expected for the growth of CNTs. Contrary to the eutectic transformation, this process occurs over a very wide temperature range of 700 C and a large carbon concentration range (50% to near 100%) within the catalyst particle. This agrees with the high carbon concentrations observed in the tungsten catalyst following CNT growth, and with the very long CNTs exceeding

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