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Fluidized-bed synthesis of sub-millimeterlong single walled carbon nanotube arrays

Article in Carbon April 2012
DOI: 10.1016/j.carbon.2011.11.032

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Fluidized-bed synthesis of sub-millimeter-long single walled

carbon nanotube arrays
Dong Young Kim, Hisashi Sugime, Kei Hasegawa, Toshio Osawa, Suguru Noda

Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

A R T I C L E I N F O

A B S T R A C T

Article history:

The rapid growth method for vertically aligned, single walled carbon nanotube (SWCNT)

Received 18 July 2011

arrays on flat substrates was applied to a fluidized-bed, using ceramic beads as catalyst

Accepted 12 November 2011

supports as a means to mass produce sub-millimeter-long SWCNT arrays. Fe/Al2Ox cata-

Available online 25 November 2011

lysts were deposited on the surface of Al2O3 beads by sputtering and SWCNTs were grown
on the beads by chemical vapor deposition (CVD) using C2H2 as a feedstock. Scanning electron microscopy and transmission electron microscopy showed that SWCNTs of 24 nm in
diameter grew and formed vertically aligned arrays of 0.5 mm in height. Thermogravimetric analysis showed that the SWCNTs had a catalyst impurity level below 1 wt.%. Furthermore, they were synthesized at a carbon yield as high as 65 at.% with a gas residence time
as short as <0.2 s. Our fluidized-bed CVD, which efficiently utilizes the three-dimensional
space of the reactor volume while retaining the characteristics of SWCNTs on substrates,
is a promising option for mass-production of high-purity, sub-millimeter-long SWCNT
arrays.
 2011 Elsevier Ltd. All rights reserved.

1.

Introduction

Impurity-free, carbon nanotubes (CNTs) have attracted great

interest because of their potential applications in CNT-based
nanotechnological fields. Especially, facile and efficient synthesis of high quality single-walled CNTs (SWCNTs) in mass
quantity has been widely studied by various groups. However,
SWCNT materials synthesized to date by chemical vapor deposition (CVD) [1], arc discharge [2], and laser ablation [3] methods
contain large quantities of impurities such as amorphous carbons and catalyst metals/supports. Moreover, SWCNTs usually
have random network morphology and short lengths in the
micrometer scale, which represent large barriers to reaching
the full potential of individual SWCNTs in practical devices
using SWCNT ensembles. In 2004, Hata et al. realized catalyst-free SWCNTs with millimeter-scale lengths as vertically
aligned arrays on catalyst supported flat substrates by a
water-assisted CVD method [4]. We systematically studied

the catalyst and CVD conditions using combinatorial methods

[5] and realized millimeter-scale growth from various feedstocks (C2H4 [6,7], C2H5OH [8], C2H2 [9,10]), even under waterfree conditions [6,9]. Despite much effort, such methods still
have unsolved problems around limited productivity caused
by the small surface area of two-dimensional substrates. Millimeter-tall SWCNTarrays grown on flat substrates are as sparse
as a few tens of g m 2.
Fluidized beds are an effective option to extend the reaction space of the reactor from two-dimensions (2D) to threedimensions (3D). CoMoCAT SWCNTs were synthesized in a
fluidized bed by Resasco and coworkers [11,12] and multiwalled CNTs (MWCNTs) are now mass produced by fluidized
bed at thousand tons per year by private companies such as
Bayer [13]. Wei and coworkers have extensively studied the
fluidized bed production of CNTs using ceramic powders as
catalyst supports [14,15] as well as the production of vertically
aligned CNT (VA-CNT) arrays on ceramics sphere supports

* Corresponding author: Fax: +81 3 5841 7332.

E-mail address: noda@chemsys.t.u-tokyo.ac.jp (S. Noda).
0008-6223/$ - see front matter  2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2011.11.032

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[16,17]. Nevertheless, mass production of (sub)millimeterlong VA-SWCNT arrays is yet to be realized.

We previously applied the rapid growth method of millimeter-tall VA-CNT arrays on flat substrates to a fluidized
bed using ceramic beads as catalyst supports [18]. The catalyst deposition, CNT growth, and CNT separation were repeated simply by switching gases while holding the beads in
the fluidized bed at a fixed temperature. This method enabled
the efficient production of high purity (99 wt.%), long
(0.4 mm), few-walled (triple on average) CNT arrays at a high
carbon yield (the ratio of carbon obtained as CNTs to that fed
to the reactor, >70 at.%) and a short gas residence time
(<0.3 s). However, difficulty in deposition of catalyst from
the metalorganic vapor in the fluidized bed was a barrier to
production of SWCNTs.
In this study, we applied the well-established sputtering
method to prepare catalyst on the beads and tried to synthesize sub-millimeter-long SWCNT arrays by fluidized bed
(Fig. 1). Fe/Al2Ox catalyst was deposited on half of the bead
surface by sputtering using a rotating sample stage and then
SWCNTs were synthesized on the beads by fluidized bed in a
batch operation. Prospects for the continuous production of
sub-millimeter-long SWCNT arrays are discussed.

2.

Experimental

Fe/Al2Ox catalyst was prepared on commercially available

Al2O3 beads (purity >99.95 wt.%, 0.5 mm average diameter,
and 3.89 g/cm3 density, Taimei Chemicals, Japan) by a sputtering method using a rotating sample stage, as shown in Fig. 1a.
The Al2O3 beads were first pretreated under O2/Ar at 1093 K for
10 min using a fluidized-bed reactor (pretreated beads). About
35 g of beads were then loaded in a monolayer on a round
groove (40 mm in width and 400 mm in diameter) on the stage
and the catalyst/support bilayer was deposited on half of their

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surface by RF magnetron sputtering via rotation of the stage at

37 rpm (Fig. 1b). The Al2Ox support layer was formed by depositing 15 nm thick Al on the pretreated beads and then exposing
the layer to air [610]. A Fe catalyst layer of 0.81.5 nm in nominal thickness was then deposited on the Al2Ox support layer on
the beads (sputtered beads). These catalyst layers were deposited on half of the bead surface and have a thickness distribution within the deposited area. The nominal thickness
represents the value at the center of the deposited area. About
70 g of the sputtered beads was loaded into a fluidized-bed
reactor consisting of a quartz tube (22 mm i.d., 900 mm length),
heated to the target temperature (1093 K, heating zone volume
of about 30 cm3), and treated under 27 kPa H2/0.06 kPa H2O/
75 kPa Ar at a flow rate of 3.16 slm (standard liters per minute)
to reduce the Fe catalyst layer and form Fe catalyst nanoparticles. The fluidized-bed CVD process was then initiated by
switching the gas to C2H2/H2/H2O/Ar to grow VA-SWCNTarrays
on half of the surface of the beads (CVD-beads) (Fig. 1b). The
standard conditions for the fluidized-bed CVD were
1.1 kPa C2H2/27 kPa H2/0.06 kPa H2O/67 kPa Ar at 3.16 slm and
1093 K, which was in the slugging regime of fluidization, as
we previously reported [18]. After CVD for 10 min, the fluidized
bed reactor was cooled down to room temperature and the CVD
beads covered with VA-SWCNT arrays were removed from the
reactor. The VA-SWCNT arrays were easily separated by shaking the CVD beads in a sample bottle by hand and then characterized by thermogravimetric analysis (TGA; Rigaku, TG8210)
in air with a heating rate of 5 K min 1 and by micro-Raman
scattering spectroscopy (HORIBA, HR 800) with an excitation laser of wavelength of 488 nm (Ar+ laser) under ambient conditions. The morphology of the VA-SWCNT arrays was observed
by field emission scanning electron microscopy (FE-SEM; Hitachi, S-4700) without separating the VA-SWCNT arrays from
the beads. Some of the VA-SWCNT arrays were transferred to
a micro grid by tweezers and analyzed by transmission electron microscopy (TEM; JEOL, 2000EX).

3.

Results and discussion

3.1.
Synthesis of VA-SWCNT arrays by fluidized bed CVD
using the sputtered beads with a fixed catalyst thickness

Fig. 1 Shematics of catalyst preparation on beads by

sputtering and growth of VA-SWCNT arrays on the beads by
fluidized bed CVD. (a) Al2Ox support layer and Fe catalyst
layer were sequentially deposited by RF magnetron
sputtering on Al2O3 beads placed into a groove on a rotating
sample stage. (b) Fe/Al2Ox catalysts were prepared and
VA-SWCNT arrays were grown on half of the spherical
surface of the beads.

First, the sputtered beads with a Fe catalyst layer of 1.5 nm in

nominal thickness were used for fluidized bed CVD. Fig. 2
shows photographs of the pretreated beads, sputtered beads,
and CVD-beads. The pretreated beads indicate typical clean,
white Al2O3 beads, while the sputtered beads indicate a dark
gray color Fe/Al2Ox catalyst/support bilayer on half of their
spherical surfaces. After fluidized-bed CVD, rough, black films
covered half of the bead surfaces, as shown in Fig. 2c. Fig. 3
shows SEM images of the pretreated beads and CVD-beads.
The pretreated beads had a smooth spherical surface
(Fig. 3a), whereas the CVD-beads had 0.5 mm tall VA-CNT arrays of various morphologies (Figs. 3be). In the enlarged image (Fig. 3f) the CNT arrays on the beads had excellent
alignment, without catalyst particles. Fig. 4 shows TEM
images and diameter distribution histograms of the synthesized CNTs, transferred from the beads to the microgrids
using tweezers without purification. The CNTs were mostly

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Fig. 2 Photographs of the pretreated beads (a), sputtered

beads (b), and CVD-beads (c).

1 wt.% and amorphous carbon of a few wt.%), and a main

burning temperature of about 860 K. This burning temperature is lower than that of the few-walled CNTs (about 920 K)
grown by fluidized bed CVD in our previous work [18], which
is consistent with the smaller number of walls in this work
(mainly single-walled) than in the previous work (triplewalled on average). We also carried out TGA under CO2 (Supplementary data Fig. S1), which also showed the small quantity of 3 wt.% for amorphous carbon.
These results, i.e. highly pure VA-SWCNT arrays with a long
length of 0.5 mm and a rather large diameter of 24 nm, are in
good agreement with those reported for CNTs grown on flat
substrates in previous studies [610]. On the other hand, the
productivity was dramatically improved. Millimeter-long VASWCNTs can be grown rapidly in 10 min in both fluidized
bed CVD and CVD on substrates but their weight was more
than 20 times larger using the fluidized bed CVD (about
0.23 g/batch) than produced on the flat substrates (typically
0.01 g/batch) using small reactors of similar volume (30 cm3).
When considering the scale up of the reactor for practical production, much higher productivity is expected for fluidized
bed CVD because the productivity is proportional to the third
order of the reactor size in fluidized bed but to the second order in CVD on flat substrates. For example, in a reactor of
l3 m3, an l m-sized square substrate provides a surface of
l2 m2 whereas d mm-sized spherical beads provides a surface
of pl3/d m2. When the reactor size is l = 1 m and the bead
diameter is d = 0.5 mm, the bead bed provides a surface of
about 600 times larger than the flat substrate.

3.2.
Effect of the catalyst thickness on the structure and
yield of VA-SWCNT arrays
SWCNTs with a rather large diameters of around 24 nm.
Most existed as individual SWCNTs or small-sized bundles
without catalyst particles.
The VA-SWCNT arrays were separated from the beads by
shaking in a sample bottle by hand and analyzed by TGA
(Fig. 5). The VA-SWCNT arrays had a high carbon purity over
99 wt.%, with only minor contamination (catalysts below

Next, sputtered beads with different nominal Fe thicknesses

(0.8, 1.0, and 1.5 nm) were used for fluidized bed CVD. Because
thinner catalyst layers result in smaller catalyst particles
[19,20], SWCNTs with smaller diameters will grow at different
yields. Fig. 6 shows the Raman spectra of VA-CNT arrays at
different positions of the beads. G-band peaks originating

Fig. 3 SEM images of the pretreated bead (a) and the beads after fluidized-bed CVD (be). The SWCNT arrays on the bead (e)
are shown at a higher magnification in (f).

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Fig. 4 TEM images of sub-millimeter-long VA-SWCNT arrays, transferred from a bead to a microgrid using tweezers, without
purification. The insets show enlarged images and the histogram of the diameter distribution of the SWCNTs.

Fig. 5 A TGA curve of the sub-millimeter-long SWCNT

arrays. VA-SWCNT arrays were separated from the beads by
shaking in a sample bottle by hand, without subsequent
purification.

from the graphite structure [21], D-band peaks originating

from disorders in the graphite structure [21], and radial
breathing mode (RBM) peaks originating from symmetric inphase displacements of carbon atoms in SWCNTs in the radial direction [21] were observed at around 1590, 1350, and
150350 cm 1, respectively. Although we can see some signature of SWCNTs in the RBM peaks, the large D-band peaks,
comparable with the G-band peaks, are different from the
usual SWCNTs with small diameters around 1 nm. This result
is typical for millimeter-tall VA-SWCNT arrays grown on flat
substrates. As we previously reported [9,22,23], Fe catalyst
particles on Al2Ox support layer become coarser during CVD,
which causes a gradual increase in the diameters of the rapidly growing SWCNTs and the abrupt termination of their
growth. SWCNTs with large diameters around 24 nm observed in the TEM image (Fig. 4) show a weak resonance with
the excitation laser at a 488 nm wavelength, and therefore
most regions of the VA-SWCNTs show Raman spectra similar
to that in Fig. 6 [9,22]. Note that the typical signature for
SWCNTs (i.e. a branched G-band peak with a small D-band

peak and clear RBM peaks) reported for millimeter-tall

VA-SWCNT arrays in early works [4,6,7] were taken at their
top surface where their diameter is the smallest. The large
D-band peak with the broad G-band peak in Fig. 6 show that
SWCNTs grown on the beads by fluidized bed had large diameters even at the top of the forests, possibly due to the higher
C2H2 concentration (1.1 vol.%) than the previous works using
flat substrates (0.10.3 vol.%) [6,7].
The spectra were generally similar within each bead and
changed more significantly for different beads accordingly
to the nominal Fe thickness at the center of the beads
(Fig. 6bd). With decreasing nominal Fe thickness, RBM peaks
became more pronounced and the G-band peak became sharper, with a shoulder at a lower wavenumber. These changes
show that the content of small-diameter SWCNTs in the
VA-SWCNT arrays was increased by decreasing the nominal
thickness of the Fe catalyst layer. But there is no clear correlation between the nominal Fe thickness and the IG/ID ratios.
For the bead with nominally 1.5 nm thick Fe, RBM peaks were
weaker and the G/D ratio was smaller at the center (nominal
Fe thickness of 1.5 nm) than the edge (nominal Fe thickness
smaller than 1.5 nm). Our previous works using flat substrates
[16,17] showed that VA-CNTs grow little below a threshold in
nominal Fe thickness (typically 0.50.6 nm) but grow to a millimeter-scale height above the threshold. Therefore, if we deposit relatively thick Fe catalyst layer (Fig. 6d), VA-SWCNTs
grow to a (sub)millimeter-scale in a wide region on the beads
with different nominal Fe thicknesses, resulting in some
broadening of the diameter distribution of SWCNTs (Fig. 4).
The effect of catalyst thickness on the yield of VA-SWCNT
arrays was examined (Fig. 7). The yield of VA-SWCNTs was
larger for thicker Fe layer, and a carbon yield as high as
65 at.% (0.23 g-SWCNT/ (0.386 g-C2H2 24/26) = 0.65) was obtained for nominally 1.5 nm thick Fe with a gas residence time
as short as <0.2 s. The amounts decreased considerably, from
0.23 to 0.09 g/batch and the carbon yield decreased accordingly from 65 to 25 at.% with decreasing nominal Fe thickness
from 1.5 to 0.8 nm (Fig. 7a). The average length of the VASWCNT arrays on the beads also decreased from 0.5 to
0.2 mm with the same decrease in nominal Fe thickness

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Fig. 6 Characterization of VA-SWCNT arrays on the Al2O3 beads. (a) A side-view schematic for the Raman measurement of
VA-SWCNT arrays on a bead. (bd) Top-view optical microscope images and Raman spectra (left: RBM region, right D-band
and G-band) of the VA-SWCNT arrays on the beads. The nominal Fe thicknesses were (b) 0.8 nm, (c) 1.0 nm, and (d) 1.5 nm.

(Fig. 7b), which is in good correlation and almost proportional

with the amount and carbon yield of CNTs. As we previously
reported, VA-SWCNT arrays grow at an almost constant rate
and then abruptly stop growing from Fe/Al2Ox catalyst for
both C2H4 [23] and C2H2 [9,10] feedstocks. Growth lifetime
but not growth rate depends on the nominal Fe thickness,
resulting in different final heights of VA-SWCNTs [9,23], and

a higher C2H2 partial pressure shortens the lifetime, especially for Fe catalysts with smaller nominal thickness [9].
The amount of Fe catalyst particles in a reactor of similar volume (30 cm3) is much larger in a fluidized bed CVD than a flat
substrate because of the much larger surface-to-volume ratio
of the catalyst support in the former. Therefore, C2H2 at a
higher partial pressure (1.1 kPa) was fed at a larger flow rate

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Fig. 7 Amounts and carbon yields of the synthesized SWCNTs (a) and average lengths of the VA-SWCNT arrays on the beads
(b) for different nominal Fe thicknesses of 0.8, 1.0, and 1.5 nm. Insets in (b) are SEM images of the VA-SWCNT arrays on the
beads, with a scale bar of 0.5 mm.

(3.16 slm) in this work than for CVD on flat substrates in previous work (0.10.6 kPa and 0.5 slm, respectively) [9]. Such a
high carbon feed can easily deactivate the catalyst by carbonization [9] and therefore water vapor at a higher partial pressure (0.06 kPa) was used than that in previous work (0
0.03 kPa) [9]. However, the excess carbon feed possibly shortened the lifetime of the small Fe particles with the thinner Fe
catalytic layer, resulted in a shorter final length and smaller
overall yield of VA-SWCNTs.

3.3.
Effects of H2O vapor on the yield and structure of
SWCNTs
Then we examined the effect of H2O vapor on the yield and
structure of SWCNTs. SWCNTs were grown at a slightly higher temperature (1113 K) to improve the quality of SWCNTs
than the experiments above while preventing sooting, with
decreasing feed of H2O vapor from 0.06 to 0 kPa (Fig. 8). The
IG/ID ratio was improved from 1.73 (B in Fig. 6b) to 2.29 (A in
Fig. 8b) with an increase in temperature by 20 K. RBM peaks
appeared at around 200 cm 1 (corresponding to 1.25 nm in
SWCNT diameter) with 0.06 kPa H2O, and they appeared at
higher wavenumbers of 200260 cm 1 with decreasing H2O
feed (Fig. 8a). The IG/ID ratio decreased from 2.29 to 1.65
(Fig. 8b and c), the average length of the SWCNT arrays decreased from 0.3 to 0.1 mm (Fig. 8d), and carbon yield decreased from 40 to 10 at.% (Fig. 8d) with decreasing H2O
feed. These results suggest that the decreased H2O feed activated small Fe particles to grow SWCNTs of smaller diameters
while it resulted in shorter growth lifetimes and degraded
SWCNT qualities. As we previously reported for flat substrates [9], H2O inhibits the SWCNT growth from thin catalytic
layer and thus small catalyst particles, possibly by oxidizing
the small catalyst particles and/or small diameter SWCNTs
of lower stability. At the same time, H2O prolongs the catalyst
lifetime when C2H2 is fed at high partial pressures [9], possibly
by removing the carbon by-products covering the catalyst particles [24]. There is a trade off in the productivity (higher
productivity with higher C2H2 and H2O feed) and SWCNT
quality (higher IG/ID ratio and smaller diameter with lower

Fig. 8 Effect of H2O vapor on the VA-SWCNT arrays grown

at 1113 K with 1.0 nm thick Fe catalyst. Raman spectra of (a)
the RBM region and (b) D-band and G-band region of the
SWCNT arrays. The partial pressures of the fed H2O vapor
were (A) 0.06 kPa, (B) 0.03 kPa, (C) 0.015 kPa, (D) 0.005 kPa,
and (E) 0 kPa. (c) The G/D ratios and (d) average lengths and
carbon yields of the VA-SWCNT arrays. Samples were made
by separating the VA-SWCNT arrays from the beads by
shaking in a sample bottle and were in a powder form.

C2H2 and H2O feed), and therefore the CVD conditions should
be chosen case by case.

3.4.
Prospects for continuous production of millimeterlong VA-SWCNT arrays
By applying a sputtered catalyst in a fluidized bed CVD, we
succeeded in synthesizing sub-millimeter-long VA-SWCNT

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arrays, which was the remaining issue from our previous

work using a catalyst deposited in situ from metalorganic vapors [18]. The amount of SWCNTs synthesized was only
0.23 g/batch but the productivity was as high as 1 kg SWCNTs
per L of reactor per day when considering a reactor volume as
small as 30 cm3 and a CVD time as short as 10 min. And the
carbon yield was as high as 65 at.% with a gas residence time
as short as <0.2 s. These achievements show that sub-millimeter-long VA-SWCNT arrays can be mass produced if catalyst particles of a suitable size can be prepared efficiently on
the beads. However, the sputtering method has a much lower
productivity (several hours for 35 g of beads) than the fluidized bed CVD (10 min for 70 g of beads) and scale-up for practical mass production makes this difference even larger
because sputtering is a 2D process, whereas the fluidized
bed CVD is a 3D process. Wet processes such as impregnation-calcination are widely used to prepare catalysts on
ceramic powders for fluidized bed CVD because of their high
productivity but are yet to produce (sub)millimeter-long
VA-SWCNT arrays. The in situ catalyst deposition by CVD from
metalorganic vapors used in our previous work [18] has a high
productivity and we are now attempting to gain control in this
process over the catalyst particle structure as fine as that possible by the sputtering method.

4.

Conclusions

By applying a sputtered catalyst to fluidized-bed CVD, we

succeeded in synthesizing sub-millimeter-long VA-SWCNT
arrays in a batch operation. The resultant VA-SWCNT arrays
had a long length (0.5 mm), a rather large diameter (2
4 nm), and high carbon purity (>99 wt.%), which are comparable to those grown on flat substrates. Furthermore, they
were synthesized at a carbon yield as high as 65 at.% with
a gas residence time as short as <0.2 s. The combination of
sputtering with fluidized bed CVD is effective for preparation
of VA-SWCNTs in gram-scale for use in basic studies but
scale-up for mass production is limited because of the poor
productivity of the sputtering method. The fine control over
the structure of the catalyst particles prepared by wet-processes or the in situ deposition process from metalorganic
vapor is the key to mass produce (sub) millimeter-long VASWCNT arrays by fluidized bed CVD. Work on this aspect is
now underway.

Acknowledgements
We gratefully thank Ms. Asuka Tashiro for her help in some
experiments. This work is financially supported by Nanotech
Challenge (No. 07005623-0) by NEDO, Japan, by cooperative research project with Hitachi Chemical, Co., Ltd., Japan, by
KAKENHI (Nos. 18686062 and 21686074), by MEXT, Japan,
and by ALCA by JST, Japan.

Appendix A. Supplementary data

Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.carbon.2011.11.032.

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