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Department of Mechanical Engineering, University of Kentucky, 521 CRMS Building, Lexington, KY 40506-0108, USA
b
Department of Chemical and Material Engineering, University of Kentucky, Lexington, KY 40506-0108, USA
c
Department of Electric Engineering, University of Kentucky, Lexington, KY 40506-0108, USA
Received 14 May 2001
Abstract
A stainless steel grid baked by a propaneair premixed ame had iron, chromium and nickel oxide deposits on the
grid surface. With this grid, entangled and curved shape multi-walled carbon nanotubes (MWNTs) were harvested from
an ethyleneair diusion ame with yield rate of 3 mg/min. Nitrogen addition to the ame was found to straighten the
entangled tubes probably by lowering the ame temperature. A cobalt-electrodeposited stainless steel grid was nally
applied to the nitrogen-diluted ethylene diusion ame; well-aligned and well-graphitized carbon nanotubes consisting
of 20 nm diameter and 10 lm long element tubes were obtained. 2001 Elsevier Science B.V. All rights reserved.
1. Introduction
This is the continuation of our previous work
on carbon nanotubes. Previously, we reported
synthesis of multi-walled carbon nanotubes using
methane diusion ames and discussed the role of
iron oxide particles as the catalyst for the nanotube growth. In that Letter our focus was basic
understanding on the mechanism of carbon
nanotube formation in the ame. This Letter discusses how to eectively synthesize well-aligned
and well-graphitized carbon nanotubes using ethylene diusion ames.
Carbon nanotubes are known to possess exceptional mechanical, electrical and thermal
properties because of their high strength, low
density, and high electrical and thermal conductivity [1]. Our previous Letter [2] summarized the
current progress on dierent synthesis methods of
carbon nanotubes. Our focus in this Letter is to
use diusion ames for commercial synthesis of
multi-walled carbon nanotubes. There is a need
of study in this area, because ame synthesis of
fullerenes has been reported, but the ame synthesis of CNTs has met with little success. Some
carbon nanotubes were found in the low pressure
premixed hydrocarbon ames and diusion ames
[35]; however, the nanotube yield was too low to
be found under SEM analysis. We present here a
unique method to synthesize carbon nanotubes
without directly seeding materials into the ame.
We used our previous experimental apparatus and
established a steady and stable laminar ethylene
air co-ow diusion ame [6]. The growth mechanism of carbon nanotubes and the eect of
nitrogen addition to the fuel stream on the nanotube growth rate were studied.
0009-2614/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 ( 0 1 ) 0 0 9 5 9 - 9
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2. Experimental
A laminar ethyleneair co-ow diusion ame
was used to synthesize MWNTs. A schematic diagram of the experimental apparatus was shown in
our previous Letter [2]. Ethylene (99.5% purity)
was issued from a 1.1 cm diameter stainless steel
tube, which was surrounded by a 5 cm diameter
tube through which air owed. With the average
linear fuel ow rate of 4.7 cm/s and the average
linear airow rate of 63 cm/s, a steady and stable
laminar ame with a visible ame height of 33 mm
was established on the burner port. All syntheses
were performed at normal atmospheric pressure. A
stainless steel grid (type 304) was used as the
substrate for the nanotube growth. The material
deposited on the wire was examined directly by
SEM (Hitachi S900, 3 kV). The deposit material
was dispersed in ethanol using a mild sonication.
Drops of the dispersion were placed on the copper
TEM grids and dried for TEM analysis (JEOL
JEM-2000-FX, 200 kV). TEMEDX (energy dispersive X-ray) analysis was performed using an
Oxford INCA detector attached to the TEM. A
high-resolution TEM (JEOL 2010F, 200 kV) was
also employed to study the microstructure of carbon nanotubes.
3. Results and discussion
When the stainless steel grid was inserted into
the ame 4 mm above the exit port without any
pre-treatment, and kept there for 10 min, some
black material deposited on the grid. There were
no nanotubes found under SEM analysis; however
some MWNTs were found under TEM analysis.
Most of the deposit material was amorphous soot
particles. This indicates that the metal oxide (iron
oxide and nickel oxide) particles formed on the
metal surface were not suitable as the catalyst
particles for carbon nanotube growth. In our
previous study, a NiCr wire was placed in the
laminar methane diusion ame for 10 min; the
formed nickel oxide particles were favorable for
the carbon nanotube growth [2]. The formation of
iron oxide was faster than that of nickel oxide; the
morphology of iron oxide layer on the metal sur-
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Fig. 1. SEM (a) and TEM (b) images of carbon nanotubes synthesized from an ethylene diusion-ame using a stainless steel sampling
grid coated with catalyst particles created by a premixed propane ame (magnication is shown in each gure).
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Fig. 2. SEM (a) and TEM (b) images of carbon nanotubes synthesized from a nitrogen-diluted ethylene diusion-ame using a
stainless steel sampling grid coated with catalyst particles created by a premixed propane ame (magnication is shown in each gure).
(a)
(b)
Fig. 3. SEM (a) and TEM (b) images of carbon nanotubes synthesized from an ethylene diusion-ame using a cobalt-coated stainless
steel grid (magnication is shown in each gure).
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images. Experimental results showed that the diameters of carbon nanotubes were well correlated
with the diameters of catalyst particles [9]. The
smaller catalyst particles generated smaller nanotubes. Because the metal oxide particles were
strongly bonded to each other, no catalyst particles could be pushed up to encapsulate nanotubes.
For the nanotube growth out of cobalt particles, TEMEDX spectra conrm the existence of
cobalt and oxygen. Some of the cobalt may be
oxidized in the ame. Fig. 3a SEM image of carbon nanotube synthesized from cobalt particles
shows no obvious particles or block of particles
attached to the tubes that were observed in the
propane-oxidized grid sampling. Fig. 3b TEM
image also displays no catalyst particles encapsulated inside the nanotubes indicating a strong
bond between the cobalt catalyst particles and the
metal surface. Fig. 5 high-resolution TEM image
shows that the nanotubes synthesized from our
ethylene ame have been well graphitized.
The production rate of MWNT is very sensitive
to the sampling location. With an increase of the
sampling location above the current location, the
concentration of pyrolyzed hydrocarbon products
increased. Some of the pyrolyzed hydrocarbon
products can be decomposed by catalyst particles,
but the rest will produce amorphous carbons, a
contaminant for catalyst particles.
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4. Conclusions
With a stainless steel grid as the substrate and
oxidized by a premixed propane ame, entangled
nanotubes with diameters ranging from 10 to 60
nm were formed from a laminar ethyleneair diffusion ame. The yield rate of the nanotubes from
our current laboratory apparatus was approximately 3 mg/min. Well-aligned and well-graphitized multi-walled carbon nanotubes consisting of
nearly uniform diameter nanotubes were synthesized from a nitrogen diluted laminar ethyleneair
diusion ame with a cobalt-electrodeposited
stainless steel grid.
Acknowledgements
This study was sponsored by National Science
Foundation under the MRSEC program (DMR-