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Ind. Eng. Chem. Res. 2008, 47, 76867692

Process Parameter Interaction Effects during Carbon Nanotube Synthesis in Fluidized Beds
Chee Howe See,* Oscar M. Dunens, Kieran J. MacKenzie, and Andrew T. Harris
Laboratory for Sustainable Technology, School of Chemical and Biomolecular Engineering, UniVersity of Sydney, Australia, NSW 2006

The interaction effects between temperature, catalyst properties, uidization conditions, and deposition time during carbon nanotube (CNT) synthesis by chemical vapor deposition in a uidized bed were investigated. While numerous investigations have attempted to correlate process parameters with CNT characteristics, selectivity and yield, the interaction between process parameters is often ignored. Parametric interactions in this process have been investigated using a factorial design methodology. Besides the main effects of synthesis temperature, deposition time, and catalyst type, the interaction parameters temperature-time and temperature-catalyst were found to signicantly inuence the resultant carbon and CNT yields. These results lay the foundation for a detailed parametric analysis toward the optimization of CNT synthesis in uidized beds, which takes into account these interaction effects.
1. Introduction Carbon nanotubes (CNTs) have been investigated for a multitude of applications including energy storage,1 eld emission devices,2 and composite material strengthening,3 because of their unique mechanical, optical, and electrical properties.4 Both multiwalled (MWCNTs) and single-walled (SWCNTs) carbon nanotubes can be used, depending on the value-added functionality required in the product. Nevertheless, the use of CNTs in both research and end-use applications is currently inhibited by production throughput.5 Of the three dominant techniques used for CNT synthesis, that is, laser ablation, arc discharge, and chemical vapor deposition (CVD), the latter is recognized as having the most potential for large-scale, economically viable CNT production.6,7 In particular, we concur with De Jong and Geus8 that the most likely low cost scenario for CNT production is to conduct the CVD reaction in a uidized bed reactor. The most prominent advantages of uidized bed CVD (FBCVD) compared to traditional xed-bed CVD are the enhanced heat and mass transfer, continuous operation, and scalability; characteristics which lead to lower costs of production.9 Despite its potential, we highlighted in a recent review, the dearth of research investigating the (FBCVD) technique for large-scale CNT capability.10 When the results of several studies are analyzed collectively,7,9-20 there appears to be no clear correlation between the synthesis parameters and CNT characteristics, yield, and selectivity. Taken to an extreme, this suggests that the synthesis of CNTs in a uidized bed is a noncontrollable process. This is almost certainly incorrect, runs counterintuitive to the behavior of similar uidized bed processes, and at the very least, requires verication. Hence, in this work, we have undertaken an experimental study to elucidate the inuential parameters; employing a statistical experimental design methodology to investigate the inuence of (i) synthesis temperature, (ii) deposition time, (iii) catalyst type (Fe, Fe-Co), (iv) catalyst loading (2.5, 5 wt %), and (v) total gas ow rate on carbon yield in a 0.5 kg/h FBCVD process.
* To whom correspondence should be addressed. E-mail: c.see@ usyd.edu.au. Tel.: +61-2-9036-6244. Fax: +61-2-9351-2854.

Although fractional factorial design (FFD) has been employed in CNT research previously,21-23 we report for the rst time, the use of this methodology for CNT synthesis via FBCVD. The advantage of using FFD is that statistically meaningful insights can be obtained using a reduced experimental set. Furthermore, besides the main effects, interaction effects (between different process parameters) can be analyzed simultaneously. In addition, the FFD design tool provides a simple validity test of the optimal parametric envelope during reactor scale-up, again using minimal experiments. We note that, to our knowledge, this is the rst time that process interaction effects have been investigated for CNT synthesis via FBCVD, although this information may well exist in a commercial environment. The results from this study verify the degree of inuence of process parameters and their interactions on the desired output criteria, laying the foundation for future detailed parametric analyses toward the optimization of CNT synthesis via FBCVD. 2. Experimental Details A typical apparatus setup is shown in Figure 1. The 52 mm internal diameter, 1000 mm long cylindrical uidized bed, constructed entirely of Inconel 601 and enclosed within a high temperature furnace, was operated as a batch reactor in this study. It has an approximate capacity of 0.5 kg CNT/h. While this diameter is less than the required minimum for many classical uidized bed scale-up rules-of-thumb, rig commissioning uidization tests show that well-developed uidization occurs, and the diameter is sufciently large to negate the substantial wall effects of very small reactors (e.g., 6.4 mm)16 without requiring impracticably large catalyst volumes. An expansion unit, 100 mm in diameter and 500 mm long, was afxed to the top of the reactor to minimize particle entrainment. Particle scrubbers were incorporated to treat efuent gases prior to release. Gas ow to the reactor was controlled via a series of Alicat Scientic, Series 16 mass ow controllers. Catalysts were prepared using impregnation.24 In brief, a weighed amount of sieved calcined alumina (-90 m, +106 m) substrate was added to an ethanolic solution of Fe or Fe-Co salts in the appropriate proportions to result in either Fe or Fe-Co (1:1) catalyst, with a total metal loading of either

10.1021/ie701786p CCC: $40.75 2008 American Chemical Society Published on Web 09/20/2008

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Figure 1. Sketch of the uidized-bed reactor setup. A cylindrical reactor is afxed within a high-temperature furnace with temperature, pressure, and gas ow controls, connected to a data logging system, as described in ref 10.

2.5 or 5 wt %. These metal loadings are representative of ratios reported in the literature.15,25 The mixture was air-dried overnight at 40 C prior to calcination in air for 12 h at 900 C. Approximately 80 ( 5 g of calcined catalyst was used in each experiment, corresponding to an initial bed height of 38 ( 2 mm. This was reduced in situ at 700 C in 1.5 SLPM, 30% H2/N2 for 1 h before ethylene (the carbon source) was introduced. The synthesis of CNTs was carried out according to the conditions depicted in the full factorial design given in Table 1, investigating the effect of (i) synthesis temperature (600 or 800 C), (ii) deposition time (20 or 60 min), (iii) catalyst type (Fe or Fe-Co), (iv) catalyst loading (2.5 or 5 wt %), and (v) total gas ow rate, reported as the ratio of the gas velocity through the bed to the minimum uidization velocity at 800 C under N2 (U/Umf ) 3 or U/Umf ) 6). The output variables were the total carbon yield, dened as TGA weight loss occurring in the temperature range 250-800 C, and carbon nanotube yield as dened in section 3. A total of 32 runs were conducted in randomized order. The as-synthesized products were analyzed using thermogravimetric analysis (TGA; TA Instruments SDT Q600), transmission electron microscopy (TEM; Philips CM120, 120 kV) and Raman spectroscopy. For TGA analysis, a sample weight of 60 mg was used. The large sample size was chosen to negate the effects of instrument error across the board, because in some instances a weight loss of <2% was obtained; this indicated that the set of conditions investigated were not conducive to CNT synthesis. A temperature ramp rate of 15 C/min and an air sweep of 50 mL/min were employed. For TEM analysis, approximately 10 mg of as-synthesized product was dispersed in 50 mL of ethanol,

Table 1. Full Factorial Design Table Investigated in This Study A B C D E A B C D E A B C D E A B C D E Variables temperature (C) uidization ratio (U/Umf) deposition time (min) catalyst loading (wt %) catalyst type ---++-+++ +-+++ +-+ +++++ ++---+-++ ----+++ +-+ --+ ----ID A B C D E (-) 600 3 20 2.5 Fe (+) 800 6 60 5 Fe-Co (1:1) ----+-+-+ ++--+ ++----+++ +++++ -+-+-++-+++----++ ----+-+-+ --+++++-+++++++++ -+-++--++ -++--++++

assisted with ultrasound. A drop of this mixture was then placed onto a 200 mesh copper grid and dried in air for 1 h prior to analysis. Raman spectroscopy was conducted using argon

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Figure 2. First order derivatives of the weight loss prole measured using TGA, showing the denition of the amorphous carbon, CNTs/CNFs, and graphitic particle regions. 2(a) and (c) are samples synthesized via FBCVD, whereas (b) is a commercial sample courtesy of Nanolabs, USA. A variety of curves are obtained depending on the ratio of individual components present within the sample.

excitation at 488 nm, 0.12 mW, for an exposure time of 20 s and 10 accumulations. An average of ve different points per sample was used. 3. Results and Discussion In this work, we have investigated the effects of ve inuential parameters (synthesis temperature, catalyst type and loading, uidization conditions, and deposition time), and their interactions, on the resulting carbon yield. To differentiate carbon yield from CNT yield using TGA, we have used the method rst described by See and Harris.26 This involves deconvoluting the TGA weight loss prole into three general groupings: (i) amorphous carbon, (ii) CNT and carbon bers, and (iii) graphitic particles. The temperature ranges of these groups have been subjectively determined on the basis of extensive TEM imaging and Raman spectroscopy of several commercial samples and subsequently utilized as a quantitative measure of each constituent. Rather than addressing the quality of product solely on the basis of the maximum burnoff temperature, which is highly dependent on the heating rate and impurities present (e.g., residual catalyst metals), this technique attempts to quantify the amount of the constituent components contributing to the overall weight loss prole. This is best illustrated by the rst order derivative of the weight loss prole, shown in Figure 2. TEM images of CNT samples corresponding to the rst order derivatives in Figure 2 are illustrated in Figure 3. The rst order derivative shown in Figure 2b, obtained using a commercial MWCNT sample (courtesy of Nanolabs; 95% purity) was used as a model MWCNT sample. The key features of the derivative function for a well-graphitized MWCNT sample (Figure 3b) are (i) the relatively narrow peak width, (ii) high maximum burnoff temperature and (iii) onset

temperature. The shape of the curve (rate of change) is similar to a process function undergoing a forcing function (constant heating rate). A width at half-peak of 54 C was obtained for this sample. A broadening of the width at half-peak to 82 C in Figure 2a suggests that a higher ratio of amorphous carbon and graphitic particles are present. The lower maximum burnoff temperature and pronounced skew toward lower temperatures was most likely due to a higher concentration of amorphous carbon and/ or poorly graphitized CNTs; this cannot be differentiated using this technique. The even larger width at half-peak of 125 C in Figure 2c suggests that a broad range of products is present, and that the CNT/CNF component is rather low. The maximum burnoff temperature of 538 C compared to the pure CNT sample of 602 C is indicative of the higher amorphous content in the sample. While we acknowledge that the oxidization range 420-620 C is a quantitative measure of both CNTs and CNFs, we refer to the weight loss in subsequent discussion as CNTs. The reason for this simplistic categorization is analysis of TEM images shows the majority of carbon product comprises CNTs. While we concede that the error is potentially large using this approach, the results are inherently more accurate than those studies based solely on TEM or Raman spectroscopy to quantify the yield of these components. It is generally accepted that TGA is the only tool capable of quantitatively measuring the yield, thermal stability, and homogeneity of a product sample.27-29 Because of the large TGA sample size required as previously noted, heat and mass transfer effects are introduced. Further optimization work, where CNT yields are substantially higher, allow the sample mass to be greatly reduced and hence this characterization protocol will provide far greater resolution. Nonetheless, more work is necessary to tune the

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Figure 3. Panels a and c are representative TEM images of CNTs synthesized via FBCVD in this work, whereas panel b is a commercial sample courtesy of Nanolabs, USA. A higher degree of graphitization is observed in panel b than in panel a, which accounts for the higher maximum burnoff temperature, in the absence of graphitic particles in signicant amounts. (c) Samples containing ill-dened nanotubes (amorphous-like) and large diameter bers exhibit lower maximum burnoff temperatures with large-peak widths.

TGA results with qualitative tools, especially in the region dened between 420 and 620 C, in order to determine the quality of CNTs formed. Raman spectroscopy was conducted on samples exhibiting a CNT-like TGA rst order derivative to determine the degree of graphitization. This is measured as the ratio between the graphite (G band, 1590 cm-1) and amorphous (D band, 1370 cm-1) Raman shifts. Typical Raman shifts of samples exhibiting TGA weight loss behavior to Figure 2a,b are correspondingly shown in Figure 4 a,b. The G/D ratio of 1.1 obtained is comparable to reported values.30,31 However, Raman spectroscopy was carried out only on samples with CNTs detected using TEM and TGA because Raman spectroscopy does not differentiate between the graphitic structures of CNTs, bers, and graphitic particles. Consequently,

Figure 4. Raman shift of (left) CNT samples synthesized via FBCVD and (right) commercial sample synthesized via CVD. The lower G/D ratio of 1.11 obtained in the left panel compared to 1.67 in the right panel suggest that the samples synthesized via FBCVD are less graphitized than the commercial sample.

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Figure 5. The gradient of ascent obtained for the four catalysts, Fe (2.5% and 5%) and Fe-Co (2.5% and 5%) weight loading on alumina, as a function of uidization ratio and deposition time, with increasing temperature: (---) CNT yield; (s) carbon yield.

high G/D ratios could possibly reect the quantity of graphitic particles present and not the quality of CNTs. Likewise, a high D band may be due to the presence of a large quantity of amorphous carbon. 3.1. Design Methodology. A full factorial design was employed in this work to verify the inuence of (i) synthesis temperature, (ii) deposition time, (iii) catalyst type (Fe, Fe-Co), (iv) catalyst loading (2.5, 5wt %), and (v) total gas ow rate, on carbon and CNT yield (TGA weight loss from 420 to 620 C was attributed as CNT yield). The factorial design was also used to examine the effect of higher order process interactions. We found that third- and fourth-order interaction effects were statistically insignicant, agreeing with most reported chemical processes.21 However, second-order interactions were not negligible and required further investigation. We stress the importance of second-order interaction effects because, in the vast majority of the literature, including parametric studies of CNT synthesis, for example, Venegoni et al.7 and Corrias et al.,15 researchers employ the change one factor at a time approach. However, not enough data is provided to analyze the effect of interactions because of the underlying assumption that the single variable at some initial xed condition is optimized. While this could have been solved iteratively as a multimodal optimization process, in the case of the studies above, the authors do not explicitly state why their starting point was optimal. Hence, the reported relationships between process variables and their optimized parameter are not generally valid unless parameter interactions are not dominant. Although the factorial design is a useful tool, it is important to account for possible discontinuities in the system under study. In this work, it is clear that the different catalyst types may

cause discontinuities, for example, there may be an inactive catalyst. Hence, it is more suitable to consider the catalysts as categorical variables. Consequently, the system should be considered as either a (i) 2 2v5-1 design based on Fe or Fe-Co catalysts or a (ii) 4 23 design by combining catalyst loading and type, rather than as a full 25 factorial design. We decided to use the latter for analysis. 3.2. Inuence of Process Variables on Carbon and CNT Yield. On the basis of the 4 23 design, we have combined the catalyst type and loading as a new parameter for analysis, which we simply call catalyst in the following discussion. The results summarized in Figure 5 suggest that all ve processes parameters investigated in this work inuence both the carbon and CNT yields signicantly. In Figure 5, the carbon and CNT yields have been normalized per unit weight of metal catalyst. This was done to prevent skewing the results in favor of higher metal loadings in the event that catalyst loading was limiting carbon deposition under the same conditions. Temperature has been reported to inuence the formation of CNTs greatly, although the effect of temperature on CNT diameter, quality, and yield remains unclear.10 On the basis of reports utilizing xed-bed reactors, it appears that the cause of such discrepancies lies in the surface area available for heterogeneous reactions to take place. Zeng et al.32 showed that under the same conditions, the carbon yield was increased simply by spreading the same amount of catalyst over a larger area, that is, using two quartz boats instead of one. This is strongly indicative of heat and mass transfer limitations. In our work, we observed a positive gradient for both carbon and CNT yield with an increase in temperature, as a function of uidization ratio and deposition time for all catalysts. However, the slope of carbon yield increases more rapidly than that for CNT

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yield, across all experiments, with an increase in temperature. This suggests that the selectivity toward CNTs decreases with increasing temperature. Nonetheless, we note that higher temperatures have been reported to produce better graphitized CNTs.26 Hence, it is necessary to consider the tradeoff between yield, quality, and selectivity to CNTs. Intuitively, one would expect that the quantity of carbon deposited would increase with deposition time. If it could be assumed that there is no lag time for CNT growth as reported by Morancais et al.,31 we would expect that when the deposition time is lengthened by three times, the carbon yield would also increase ca. three times, in the absence of inhibiting factors, for example, catalyst deactivation. However, there does not appear to be a correlation across the board between the gain in carbon yield with deposition time; gains from 1 (Fe 2.5%, U ) 3Umf, 600 C) to 13 (Fe 2.5%, U ) 6Umf, 800 C) were observed with an increase in deposition time, which suggests that a lag probably does exist. If the rate of carbon deposition was a function of the activated state of the catalysts, then the rate of carbon deposition should decrease over time because of catalyst deactivation. Thus, the gain of carbon deposited should decrease over time. However, in a few instances, a gain much greater than the increase in deposition time was obtained. Therefore, it is probable that carbon deposition slows during the rst 20 min; perhaps a lag time exists, or the rate of carbon gasication is quicker. Nonetheless, a more pronounced increase in carbon yield is observed for experiments conducted at the higher uidization ratio than at the lower ratio with increasing deposition time. This seems to suggest that the higher gas ow rate induced better mixing, leading to greater heat and mass transfer between solid and gas particles. This is true of most uidized bed processes operating in the bubbling uidization regime.33 For a deposition time of 60 min, we observed an increase in carbon yield as the uidization ratio was doubled. Although a doubling in the carbon yield was expected since the total carbon feed was also doubled, we observed an increase of less than 2 times. In contrast, a general decrease in carbon yield for a catalyst loading of 2.5%, for a deposition time of 20 min, was observed. This counterintuitive observation can also be attributed to the uncertainty as to whether or not there is a lag time before CNT synthesis begins. An analysis of variance (ANOVA) was conducted at a 95% condence interval to verify the statistical signicance of process parameters using both carbon and CNT yields as the parameters for optimization. It was found that there was sufcient data for the analysis to be statistically valid in both response variables (i.e., model P < 0.05) and the main effects; that is, (i) synthesis temperature, (ii) run duration, and (iii) catalyst, and second-order effects, (iv) temperature-time and (v) temperature-catalyst, were signicant. The results of the ANOVA are given in Table 2. The insignicance of uidization ratio in the experimental runs suggests that the experiments were likely conducted in the same uidization regime. Therefore, the heat and mass transfer coefcients are somewhat comparable for both ow rates investigated. Nonetheless, the actual uidization regime at which the experiments were undertaken is uncertain. This can be attributed to changes in (i) gas density and viscosity of the reactive gas mixture, (ii) rate of reactions, and (iii) bed stability. We have observed in further experiments (See, C. H.; Harris, A. T. Large-scale production of multiwalled carbon nanotubes by uidized bed chemical vapor deposition: Parametric investigation of interaction pairs, In preparation) that while the ow rates employed were at the respective uidization ratios under

Table 2. ANOVA for Selected Factorial Model Analysis of Variance Table [Classical Sum of Squares, Type II]a response 1: carbon yield source model A, temperature B, U/Umf C, deposition time D, catalyst AB AC AD BC BD CD R2 F value 6.3 41.3 3.1 28.8 1.1 0.2 23.6 3.1 2.9 0.2 0.261 0.898 p-value prob > F <0.001 <0.001 0.100 <0.001 0.380 0.608 <0.001 0.065 0.112 0.904 0.8524 response 2: CNT yield F value 5.7 25.7 1.4 25.3 4.5 0.02 9.3 5.0 2.3 1.7 1.788 0.888 p-value prob > F 0.001 <0.001 0.254 <0.001 0.023 0.889 0.009 0.016 0.153 0.225 0.199

a ANOVA of carbon and CNT yields. A value of P < 0.05 indicates a statistically signicant variable. These are highlighted in bold.

nitrogen, this is not the case during the CNT deposition reaction. A step change in carbon yield was observed at about U/Umf ) 15, which we believe is the actual start of the bubbling regime under typical reaction conditions in our setup. Hence, the ow rate that was employed is likely to be bordering on the intermediate uidization regime, that is, close to Umf. The catalyst type and their interaction with temperature was found to have a signicant effect on CNT yield only, signifying that the selectivity of CNTs over other carbon products is highly dependent on the catalyst used. This is why numerous catalysts have been investigated to date.34 In our work, it appeared that a higher carbon yield per unit weight of metal was obtained for 2.5 wt % loadings than for 5 wt % loadings, regardless of catalyst type. However, the binary Fe-Co catalysts seem to be more selective toward CNTs than the singular Fe catalyst. 4. Conclusions We have investigated for the rst time, the effect of parametric interactions on carbon and CNT yield for CNT synthesis via FBCVD. This was achieved using a full factorial design investigating the effects of (i) synthesis temperature, (ii) deposition time, (iii) uidization ratio, and (iv) catalyst. Besides the main effects of synthesis temperature, deposition time, and catalyst, the interactions between temperature-time and temperature-catalyst were found to inuence both CNT and carbon yield. The effects of interaction parameters have not been adequately studied in the literature to date, even during parametric studies of CNT synthesis. The work reported here forms the basis for further in-depth parametric analytical studies investigating both main effects and two-factor interactions. Acknowledgment C.H.S. gratefully acknowledges the nancial support of the Commonwealth of Australia and the University of Sydney for providing the Endeavour International Postgraduate Research Scholarship and International Postgraduate Award respectively. The authors are grateful to Nanolabs (USA) for providing CNT samples for comparative analysis. Literature Cited
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ReceiVed for reView December 31, 2007 ReVised manuscript receiVed March 26, 2008 Accepted August 12, 2008 IE701786P