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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 elec-
tron microscopy and transmission electron microscopy showed that SWCNTs of 2–4 nm in
diameter grew and formed vertically aligned arrays of 0.5 mm in height. Thermogravimet-
ric analysis showed that the SWCNTs had a catalyst impurity level below 1 wt.%. Further-
more, 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.
[16,17]. Nevertheless, mass production of (sub)millimeter- surface by RF magnetron sputtering via rotation of the stage at
long VA-SWCNT arrays is yet to be realized. 37 rpm (Fig. 1b). The Al2Ox support layer was formed by depos-
We previously applied the rapid growth method of milli- iting 15 nm thick Al on the pretreated beads and then exposing
meter-tall VA-CNT arrays on flat substrates to a fluidized the layer to air [6–10]. A Fe catalyst layer of 0.8–1.5 nm in nom-
bed using ceramic beads as catalyst supports [18]. The cata- inal thickness was then deposited on the Al2Ox support layer on
lyst deposition, CNT growth, and CNT separation were re- the beads (sputtered beads). These catalyst layers were depos-
peated simply by switching gases while holding the beads in ited on half of the bead surface and have a thickness distribu-
the fluidized bed at a fixed temperature. This method enabled tion within the deposited area. The nominal thickness
the efficient production of high purity (99 wt.%), long represents the value at the center of the deposited area. About
(0.4 mm), few-walled (triple on average) CNT arrays at a high 70 g of the sputtered beads was loaded into a fluidized-bed
carbon yield (the ratio of carbon obtained as CNTs to that fed reactor consisting of a quartz tube (22 mm i.d., 900 mm length),
to the reactor, >70 at.%) and a short gas residence time heated to the target temperature (1093 K, heating zone volume
(<0.3 s). However, difficulty in deposition of catalyst from of about 30 cm3), and treated under 27 kPa H2/0.06 kPa H2O/
the metalorganic vapor in the fluidized bed was a barrier to 75 kPa Ar at a flow rate of 3.16 slm (standard liters per minute)
production of SWCNTs. to reduce the Fe catalyst layer and form Fe catalyst nanoparti-
In this study, we applied the well-established sputtering cles. The fluidized-bed CVD process was then initiated by
method to prepare catalyst on the beads and tried to synthe- switching the gas to C2H2/H2/H2O/Ar to grow VA-SWCNTarrays
size sub-millimeter-long SWCNT arrays by fluidized bed on half of the surface of the beads (CVD-beads) (Fig. 1b). The
(Fig. 1). Fe/Al2Ox catalyst was deposited on half of the bead standard conditions for the fluidized-bed CVD were
surface by sputtering using a rotating sample stage and then 1.1 kPa C2H2/27 kPa H2/0.06 kPa H2O/67 kPa Ar at 3.16 slm and
SWCNTs were synthesized on the beads by fluidized bed in a 1093 K, which was in the slugging regime of fluidization, as
batch operation. Prospects for the continuous production of we previously reported [18]. After CVD for 10 min, the fluidized
sub-millimeter-long SWCNT arrays are discussed. bed reactor was cooled down to room temperature and the CVD
beads covered with VA-SWCNT arrays were removed from the
2. Experimental reactor. The VA-SWCNT arrays were easily separated by shak-
ing the CVD beads in a sample bottle by hand and then charac-
Fe/Al2Ox catalyst was prepared on commercially available terized by thermogravimetric analysis (TGA; Rigaku, TG8210)
Al2O3 beads (purity >99.95 wt.%, 0.5 mm average diameter, in air with a heating rate of 5 K min 1 and by micro-Raman
and 3.89 g/cm3 density, Taimei Chemicals, Japan) by a sputter- scattering spectroscopy (HORIBA, HR 800) with an excitation la-
ing method using a rotating sample stage, as shown in Fig. 1a. ser of wavelength of 488 nm (Ar+ laser) under ambient condi-
The Al2O3 beads were first pretreated under O2/Ar at 1093 K for tions. The morphology of the VA-SWCNT arrays was observed
10 min using a fluidized-bed reactor (pretreated beads). About by field emission scanning electron microscopy (FE-SEM; Hit-
35 g of beads were then loaded in a monolayer on a round achi, S-4700) without separating the VA-SWCNT arrays from
groove (40 mm in width and 400 mm in diameter) on the stage the beads. Some of the VA-SWCNT arrays were transferred to
and the catalyst/support bilayer was deposited on half of their a micro grid by tweezers and analyzed by transmission elec-
tron microscopy (TEM; JEOL, 2000EX).
Fig. 3 – SEM images of the pretreated bead (a) and the beads after fluidized-bed CVD (b–e). The SWCNT arrays on the bead (e)
are shown at a higher magnification in (f).
CARBON 5 0 ( 20 1 2 ) 1 5 3 8–15 4 5 1541
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. 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. (b–d) 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 a higher C2H2 partial pressure shortens the lifetime, espe-
with the amount and carbon yield of CNTs. As we previously cially for Fe catalysts with smaller nominal thickness [9].
reported, VA-SWCNT arrays grow at an almost constant rate The amount of Fe catalyst particles in a reactor of similar vol-
and then abruptly stop growing from Fe/Al2Ox catalyst for ume (30 cm3) is much larger in a fluidized bed CVD than a flat
both C2H4 [23] and C2H2 [9,10] feedstocks. Growth lifetime substrate because of the much larger surface-to-volume ratio
but not growth rate depends on the nominal Fe thickness, of the catalyst support in the former. Therefore, C2H2 at a
resulting in different final heights of VA-SWCNTs [9,23], and higher partial pressure (1.1 kPa) was fed at a larger flow rate
CARBON 5 0 ( 20 1 2 ) 1 5 3 8–15 4 5 1543
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 pre-
vious work (0.1–0.6 kPa and 0.5 slm, respectively) [9]. Such a
high carbon feed can easily deactivate the catalyst by carbon-
ization [9] and therefore water vapor at a higher partial pres-
sure (0.06 kPa) was used than that in previous work (0–
0.03 kPa) [9]. However, the excess carbon feed possibly short-
ened 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.
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